Hindered amine light stabilized polymer compositions

ABSTRACT

Hindered amine light stabilizers are provided in which the hindered amine is contained in a unit of formula ##STR1## where X is ##STR2## and R 1 , R 2 , R 3  and A are as defined as in the Summary of the Invention. Unique polymeric and non-polymeric compounds containing this unit are useful as additives for the stabilization of polymeric compositions which are normally subject to thermal, oxidative or actinic light degradation.

CROSS-REFERENCE TO RELATED APPLICATION

This is a division of copending U.S. patent application Ser. No.08/112,749, filed Aug. 26, 1993, U.S. Pat. No. 5,408,008 which is adivision of U.S. Patent application Ser. No. 07/317,372, filed Mar. 1,1989, now U.S. Pat. No. 5,241,067, which is a continuation-in-part ofU.S. patent application Ser. No. 060,878, filed Jun. 12, 1987, nowabandoned.

BACKGROUND OF THE INVENTION

This invention relates to hindered amine light stabilizers in which thehindered amine is attached to the nitrogen of an imide which is attachedto an aromatic group containing a carboxylic acid or derivative thereof.

Hindered amine light stabilizers (hereinafter referred to as "HALS") area well-known class of compounds known to prevent and retard thedegradation of polymers in which they are incorporated (Kirk-OthmerEncyclopedia of Chemical Technology, 3rd Ed., Vol. 23, "UV Stabilizers",pp. 615-627). Many patents on HALS additives and monomers have beenissued, e.g., U.S. Pat. No. 4,336,183. The fundamental HALSfunctionality is a rather small molecular ensemble, generally watersoluble; this prohibits use of simple, low molecular weight HALS becausethey are readily leached from the polymer substrate upon exposure tomoisture.

HALS imides such as N-(2,2,6,6-tetramethyl-4-piperidinyl)maleimide areknown and have been used to prepare HALS-containing copolymers (as inU.S. Pat. No. 4,569,997 and British Patent Application Publication No.2,145,100 A). Other N-(2,2,6,6-tetramethyl-4-piperidinyl)imides aredisclosed in U.S. Pat. No. 4,356,307, but the disclosed compounds arenon-aromatic imides. N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimideand N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)pyromellitic diimidehave been disclosed as polymer stabilizers in U.S. Pat. No. 3,904,581,although neither compound was prepared nor tested.

No reference to the instant invention could be found in the literature.

Definitions

As used herein, the term "acyl" refers to a substituent derived from acarboxylic acid group by removing the OH of the carboxyl group therebyproviding a free valence, i.e. the acyl group derived from a generalizedcarboxylic acid Q--C(═O)--OH would have the formula Q--C(═O)-- and wouldbe referred to herein as a "Q acyl" group.

As used herein, the term "aliphatic," whether used alone or whenincorporated as part of another term in naming a radical, such as"aliphatic acyl" or "araliphatic," for example, denotes an organicchemical radical characterized by straight-chain or branched-chainarrangement of the constituent carbon atoms, wherein the radical has theindicated number of carbon atoms.

As used herein, the term "aryl," whether used alone or when incorporatedas part of another term in naming a radical, such as "aryl acyl" or"araliphatic," for example, denotes a carbocyclic aromatic ringstructure, wherein the radical has the indicated number of carbon atoms.

As used herein, the terms "polymer" and "polymeric composition(s)"include homopolymers or any type of copolymers.

When any generalized functional group or index, such as R¹, R², d, q,etc. appears more than once in a general formula, the meaning of each isindependent of one another.

SUMMARY OF THE INVENTION

This invention is directed to compounds of general formula ##STR3## andderivatives thereof, where R¹ is hydrogen or substituted orunsubstituted alkyl of 1-4 carbons. Preferably, R¹ is hydrogen ormethyl. Most preferably, R¹ is hydrogen. ##STR4## where

R² is oxyl, hydroxy, substituted or unsubstituted aliphatic acyl of 1-20carbons, substituted or unsubstituted alicyclic acyl of 6-14 carbons,substituted or unsubstituted aryl acyl of 7-11 carbons, substituted orunsubstituted araliphatic acyl of 7-22 carbons, --C(═O)--N(R⁴)(R⁵) or--C(═O)--O--R⁶ Preferably, R² is substituted or unsubstituted alkanoylof 2-5 carbons, aliphatic acyl of 2-5 carbons, substituted orunsubstituted aryl acyl of 7-11 carbons or substituted or unsubstitutedaraliphatic acyl of 7-22 carbons. Most preferably, R² is acetyl,substituted or unsubstituted benzoyl or --C(═O)--O--R⁶.

R³ is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted araliphatic of 7-22 carbons, alkoxyalkyl of2-21 carbons or --CH₂ --C(═O)--O--R⁷. Preferably, R³ is hydrogen,substituted or unsubstituted alkyl of 1-4 carbons, substituted orunsubstituted alkoxyalkyl of 2-6 carbons, substituted or unsubstitutedaraliphatic of 7-10 carbons, allyl or --CH₂ --C(═O)--O--R⁷. Mostpreferably, R³ is hydrogen, substituted or unsubstituted alkyl of 1-4carbons, allyl, benzyl or --CH₂ --C(═O)--O--R⁷.

R⁴, R⁵ and R⁷ are independently hydrogen, substituted or unsubstitutedaliphatic of 1-20 carbons, substituted or unsubstituted aryl of 6-10carbons, substituted or unsubstituted araliphatic of 7-22 carbons or asubstituted or unsubstituted alicyclic group of 5-12 carbons which mayoptionally contain --N(R⁹)-- as a group member and R⁴ and R⁵ mayoptionally be linked together to form an alicyclic group of 5-7 atoms ormay be linked together through a heteroatom --N(R¹⁰)-- or --O-- to forma heterocyclic ring of 5-7 atoms. Preferably, R⁴, R⁵ and R⁷ areindependently hydrogen, substituted or unsubstituted alkyl of 1-4carbons, substituted or unsubstituted cyclohexyl, substituted orunsubstituted benzyl or substituted or unsubstituted phenyl.

R⁶ is substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted aryl of 6-10 carbons, substituted orunsubstituted araliphatic of 7-22 carbons or a substituted orunsubstituted alicyclic group of 5-12 carbons which may optionallycontain --N(R⁹)-- as a group member. Preferably, R⁶ is substituted orunsubstituted alkyl of 1-6 carbons, substituted or unsubstituted aralkylof 7 to 10 carbons or substituted or unsubstituted phenyl.

R⁸ is hydroxy, O--O.sup.⊖, halogen --NH₂, --NHNH₂ or the residue from asubstituted or unsubstituted, monofunctional or polyfunctional alcohol,amine, mercaptan or hydrazine group or molecular mixture thereof,wherein hydroxy-containing and amine-containing polymers may bebackbone, pendant or terminally functionalized.

R⁹ and R¹⁰ are independently hydrogen or substituted or unsubstitutedalkyl of 1-4 carbons.

s is an integer of 1 to a number corresponding to the number of freevalences of R⁸.

A is an anion chloride, bromide, sulfate, acid sulfate, sulfite, acidsulfite, p-toluenesulfonate, phenylsulfonate, methylsulfonate,phosphate, acid phosphate, carboxylate from any carboxylic acid or R⁸when R⁸ is --O.sup.⊖.

Substituents for the alkyl, aliphatic, aryl, araliphatic, alicyclic,aliphatic acyl, aryl acyl or araliphatic acyl radicals, R¹, R², R³, R⁴,R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ independently are one or more of aliphatic of1-8 carbons, alkoxy of 1-4 carbons, alkanoyl of 1-12 carbons,alkanoyloxy of 1-12 carbons, alkoxycarbonyl of 2-5 carbons, arylcarbonylof 7-11 carbons, acryloyloxy, methacryloyloxy, aryloxy of 6-10 carbons,aralkyl of 7-10 carbons, aryloxycarbonyl of 7-11 carbons, aryl of 6-10carbons, amino, hydroxy, carboxy, nitrile, chloro, bromo, epoxy, vinyl,alkyl mercapto of 1-4 carbons, benzoyloxy, aryl mercapto of 6-10carbons, alkylamino of 1-4 carbons, dialkylamino of 2-8 carbons,arylamino of 6-10 carbons, aryl alkyl amino of 7-10 carbons ortrialkoxysilyl of 3-9 carbons.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS General Formula

The compounds of this invention are characterized by the presence of atleast one hindered amine group attached to the nitrogen of an imidewhich is also attached to an aromatic group, which also contains acarboxy group or a derivative thereof having the general formula I:##STR5## wherein R¹, R⁸, s and X are as previously defined.

Generic Group Examples.

As an alkyl of 1-4 carbons, R¹, R⁹ and R¹⁰ are independently, forexample, methyl, ethyl, propyl, isopropyl, butyl and sec-butyl.

As a substituted or unsubstituted aliphatic radical of 1-20 carbons, R³,R⁴, R⁵, R⁶ and R⁷ are independently, for example, methyl, ethyl,n-propyl, isopropyl, butyl, allyl, n-pentyl, hexyl, heptyl,2-bromoethyl, octyl, nonyl, decyl, propargyl, octadecyl, dodecyl,isododecyl, tetradecyl, methallyl, 2-hexenyl, 10-undecenyl, 2-dodecenyl,2-acetoxyethyl, 2-hydroxyethyl, 2-butenyl, 2-hydroxyhexadecyl,2-hydroxypropyl, 2-hexenyl, 10-undecenyl, 2-dodecenyl, 2-hydroxydodecyl,2-hydroxy-5-hexenyl, 2-hydroxyhexyl, 2-hydroxydecyl, 2-hydroxyoctadecyl,2-hydroxy-3-(methacryloyloxy)propyl, 2-hydroxy-3-(acryloyloxy)propyl,2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-(4-methoxyphenoxy)propyl,3-(trimethoxysilyl)propyl, 2-hydroxy-3-methoxypropyl,2-hydroxy-3-(cyclohexyloxy)propyl, 2-hydroxy-3-(benzyloxy)propyl,2-hydroxy-3-(benzoyloxy)propyl, 2-hydroxy-3-dodecyloxypropyl,2-hydroxybutyl, 1-methyl-2-hydroxypropyl, cyanomethyl, 2,3-epoxypropyl,2-(dimethylamino)ethyl or propargyl.

As a substituted or unsubstituted aryl radical of 6-10 carbons, R⁴, R⁵,R⁶ and R⁷ are independently, for example, phenyl, tolyl, 4-butoxyphenyl,2-methoxyphenyl, 4-chlorophenyl, isopropylphenyl, isopropenylphenyl,anisyl, trimethylphenyl, 4-n-octylphenyl,3,5-di(t-butyl)-4-hydroxyphenyl, 3,5-di(t-amyl)-4hydroxyphenyl,4-vinylphenyl, 3-(t-butyl)-5-methyl-4-hydroxyphenyl, naphthyl,3-methyl-5-t-butyl-4-hydroxyphenyl, 3,4,5-trimethoxyphenyl or4-dimethylaminophenyl.

As a substituted or unsubstituted araliphatic radical of 7-22 carbonsR³, R⁴, R⁵, R⁶ and R⁷ are independently, for example, benzyl,3-methylbenzyl, 4-t-butylbenzyl, cinnamyl,3,5-di-t-butyl-4-hydroxybenzyl, 2-phenoxyethyl, 2-hydroxy-2-phenylethyl,2-phenylethyl, 1-methyl1-phenylethyl, 3-phenylpropyl, trimethylbenzyl,4-octyloxybenzyl, naphthylmethyl, (4-dodecylphenyl)methyl,2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl,2-(3,5-di-t-amyl-4-hydroxyphenyl)ethyl or2-(3-t-butyl-5-methyl-4-hydroxyphenyl)ethyl.

As a substituted or unsubstituted alicyclic group of 5-12 carbons whichmay optionally contain --N(R⁹)-- as a ring member, R⁴, R⁵, R⁶ and R⁷ areindependently for example cyclohexyl, trimethylcyclohexyl, cyclooctyl,cyclododecyl, 4-t-butylcyclohexyl, 2-hydroxycyclododecyl,3-cyclohexenyl, 2-hydroxycyclohexyl, 2-hydroxycyclopentyl, cyclododecyl,4-octylcyclohexyl, 2,2,6,6-tetramethyl-4-piperidinyl,2,6-diethyl-2,3,6-trimethyl-4-piperidinyl,1,2,2,6,6-pentamethyl-4-piperidinyl, 51-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinyl or2-methyl-4-octylcyclohexyl.

As a substituted or unsubstituted aliphatic acyl radical of 1-20carbons, alicyclic acyl radical of 6-14 carbons, aryl acyl radical of7-11 carbons or araliphatic acyl radical of 7-22 carbons. R² is forexample, formyl, acetyl, chloroacetyl, acryloyl, methacryloyl,propionyl, 2-methylpropionyl, 3-phenylpropionyl, crotonoyl, butyryl,octanoyl, dodecanoyl, caproyl, capryloyl, lauroyl, stearoyl,octadecanoyl, cyclohexylcarbonyl, 4-t-butylcyclohexylcarbonyl,3-cyclohexenyl-1-carbonyl, cyclododecylcarbonyl,4-octylcyclohexylcarbonyl, 2-ethoxy-2-oxoacetyl, 2-methoxy-2-oxoacetyl,cinnamoyl, dihydrocinnamoyl, 2-methyl-4-octylcyclohexylcarbonyl,4-ethoxybenzoyl, benzoyl, chlorobenzoyl, isopropylbenzoyl,2,4-dichlorobenzoyl, toluoyl, anisoyl, 3-butoxybenzoyl,2-hydroxybenzoyl, 3,5-di-t-butyl-4-hydroxybenzoyl,3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl,3-methyl-5-t-butyl-4-hydroxybenzoyl, 3,4,5-trimethoxybenzoyl,4-(dimethylamino)benzoyl, cyclohexyl-1-carbonyl, phenylacetyl,phenethyl, 1- or 2-naphthoyl or decahydronaphthoyl.

As --C(═O)--N(R⁴)(R⁵), wherein R⁴ and R⁵ are linked together to form analicyclic group of 5-7 atoms or are linked together through a heteroatom--N(R¹⁰)-- or --O-- to form a heterocyclic group of 5-7 atoms, R² is forexample, piperidin-1-ylcarbonyl,2,2,6,6-tetramethyl-4-piperidinylcarbonyl, piperazine-1-carbonyl,4-methylpiperazine-1-carbonyl or morpholine-1-carbonyl.

As a substituted or unsubstituted alkoxyalkyl of 2-21 carbons, the alkylpart of R³ contains, for example, 1-3 carbons and the alkoxy partcontains, for example, 1-18 carbons, as in, for example, methoxymethyl,ethoxymethyl, 2-hydroxy-3-isopropoxypropyl, 2-methoxyethyl,2-ethoxyethyl, 2-t-butoxyethyl, 2-hydroxy-3-(2-ethylhexyloxy)propyl,3-t-butoxypropyl, 2-octoxyethyl or 2-octdecyloxyethyl.

R⁸ defines a derivative of the aromatic carboxylic acid group of generalformula I and as such, must contain at least one oxygen, nitrogen,sulfur or halogen atom capable of bonding to the aryl acyl group. Whenattached by an oxygen, nitrogen or sulfur of R⁸, the invention comprisesa compound containing one or more groups having the general formula Ishown above incorporated as one or more ester, amide, thioester orhydrazide groups. Mixtures of ester, amide and thioester are derivedfrom substituted or unsubstituted, monofunctional or polyfunctionalalcohol, amine, mercaptan or hydrazine groups or molecular mixturethereof, including hydroxy-containing and amine-containing polymerswhich may be backbone, pendant or terminally functionalized.

As a halogen, R⁸ is for example, chlorine or bromine; preferablychlorine.

As the residue from a substituted or unsubstituted, monofunctional orpolyfunctional alcohol, amine, mercaptan or hydrazine or molecularmixture thereof, R⁸ is for example, any of the following:

When s is 1, R⁸ is 1-morpholinyl, 1-piperidinyl, 1-pyrrolidinyl or R¹¹--Y--.

Y is --O--, --N(R¹²)--, --S--, --C(═O)--NH--NH--, --NH--NH--,--NH--C(═O)--NH--NH--, --O--C(═O)--NH--NH--,--NH--C(═O)--C(═O)--NH--NH-- or --O--C(═O)--C(═O)--NH--NH--.

R¹¹ is, for example, hydrogen, substituted or unsubstituted aliphatic of1-20 carbons, substituted or unsubstituted aryl of 6-10 carbons,substituted or unsubstituted araliphatic of 7-22 carbons, a substitutedor unsubstituted alicyclic group of 5-12 carbons which may optionallycontain --N(R¹³)-- as a group member, trialkylsilylalkyl of 5-20carbons, alkyldiarylsilylalkyl of 15-20 carbons, alkoxyalkyl of 3-20carbons, substituted or unsubstituted3-(2H-benzotriazol-2-yl)-2-hydroxybenzyl, substituted or unsubstituted4-benzoyl-3-hydroxyphenoxymethyl, substituted or unsubstituted4-benzoyl-3-hydroxyphenoxyethyl, trialkoxysilylpropyl of 4-15 carbons,substituted or unsubstituted 4-[2,2,di(methoxycarbonyl)ethenyl]phenyl orpolyalkyl having a general formula CH₃ --(CH₂)_(c) -- in which c is aninteger of 25-50.

R¹² is, for example, hydrogen, substituted or unsubstituted aliphatic of1-20 carbons, substituted or unsubstituted aryl of 6-10 carbons,substituted or unsubstituted araliphatic of 7-22 carbons or asubstituted or unsubstituted alicyclic group of 5-12 carbons which mayoptionally contain --N(R¹⁴)-- as a group member.

R¹³ and R¹⁴ are independently, for example, hydroxy, substituted orunsubstituted aliphatic acyl of 1-20 carbons, substituted orunsubstituted alicyclic acyl of 6-14 carbons, substituted orunsubstituted aryl acyl of 7-11 carbons, substituted or unsubstitutedaraliphatic acyl of 7-22 carbons, --C(═O)--N(R⁴)(R⁵), --C(═O)--O--R⁶substituted or unsubstituted aliphatic of 1-20 carbons, substituted orunsubstituted araliphatic radical of 7-22 carbons, alkoxyalkyl of 2-21carbons and --CH₂ --C(═O)--O--R⁷.

When s is 1 or more, R⁸ is any of the following polyvalent groups(i)-(xii) with the understanding that any valence not satisfied byattachment to the acyl group shown in the general formula I is satisfiedby a group R¹⁵.

R¹⁵ is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted aryl of 6-10 carbons, substituted orunsubstituted araliphatic of 7-22 carbons and substituted orunsubstituted alicyclic of 5-12 carbons, substituted or unsubstitutedaliphatic acyl of 1-20 carbons, substituted or unsubstituted alicyclicacyl of 6-14 carbons, substituted or unsubstituted aryl acyl of 7-11carbons or substituted or unsubstituted araliphatic acyl of 7-22carbons.

(i) R⁸ is 1,4-piperazindiyl.

(ii) R⁸ is --Y--R¹⁶ --Y-- wherein Y is as previously defined.

R¹⁶ is a substituted or unsubstituted aliphatic diradical of 2-20carbons, substituted or unsubstituted alicyclic diradical of 5-20carbons, substituted or unsubstituted aryl diradical of 6-10 carbons,substituted or unsubstituted araliphatic diradical of 7-22 carbons,where the aliphatic, alicyclic and araliphatic diradicals may containheteroatoms nitrogen, sulfur or oxygen, 4,4'-oxybis(phenylene)-diyl,1,2-phenylenebis(oxyalkyl) of 10-14 carbons, 1,4-phenylenebis (oxyalkyl)of 10-14 carbons, oxybis (dimethylsilylpropyl), 4,4'-biphenyldiyl,2,2-propane-bis (phenylene)-p,p'-diyl, diphenylsulfone-4,4'-diyl,poly(alkoxy)dialkyl having a general formula ##STR6## in which R¹⁷ ishydrogen, substituted or unsubstituted aliphatic of 1-20 carbons orsubstituted or unsubstituted araliphatic of 7-10 carbons and d is aninteger of 1 or 2 and e is an integer of 0-350, polycarbonate diradicalshaving a general formula ##STR7## in which f and g are independentlyintegers of 1-5 and R¹⁸ and R¹⁹ are independently a substituted orunsubstituted aliphatic diradical of 2-20 carbons, substituted orunsubstituted alicyclic diradical of 5-12 carbons, substituted orunsubstituted aryl diradical of 6-10 carbons or substituted orunsubstituted araliphatic diradical of 7-22 carbons, diester andpolyester diradicals having a general formula ##STR8## which h is aninteger of 0 to 10, unsaturated polyolefin diradicals having a molecularweight of from about 2000 to about 3500, poly(mercaptoether) diradicals##STR9## in which i is an integer of 2-12, unsaturated copolymerdiradicals having a general formula ##STR10## in which m is an integerof 5-10 and j and k are component fractions, k is about 0.1 to about 0.3and j is 1-k, poly(organosiloxane) diradicals having a general formula##STR11## in which n is an integer of 5-3000 and q is an integer of 3 or4 or polyester diradicals having a general formula ##STR12## in which bis an integer of 0-10 and may be different for each of the two repeatinggroups, and R²⁰ is an aliphatic diradical of 2 to 4 carbons.

Non-limiting examples of R¹⁶ are 1,2-ethanediyl, 1,2-propanediyl,1,3-propanediyl, 1,4-butanediyl, 1,18-octadecanediyl,2,2-dimethyl-1,3-propane-diyl, 2-methylpentane-2,4-diyl,1,10-decanediyl, 1,12-dodecanediyl, 3-oxapentane-1,5-diyl,4-oxaheptane-1,7-diyl, 3,6-dioxaoctane-1,8-diyl,4,9-dioxadodecane-1,12-diyl, 4-methyl-4-azaheptane-1,4-diyl,3,6-diaza-3,6-dimethyl-1,8-octanediyl, 3-methyl-3-azapentane-1,5-diyl,tricyclo[5.2.1.0¹,5 ]decane-3,7-diylbis(methyl), 1,2-cyclohexanediyl,1,4-cyclohexanediyl, 1,2-ethenediyl, 1,2-propenediyl,1-chloro-1,2-ethenediyl, cyclohexane-1,4-bis(methyl),1-phenyl-1,2-ethenediyl, 1,3-hexanediyl, 1,2-cyclohexanediyl,1,2-phenylene, 4-methyl-4-cyclohexene-1,2-diyl, 4-cyclohexene-1,2-diyl,4-methylcyclohexane-1,2-diyl, 4-carboxy-1,2-phenylene,4-methoxycarbonyl-1,2-phenylene, propane-2,2-bis[4-cyclohexyl],propane-2,2-bis[4-phenyl], 3-oxapentane-1,5-diyl,methylenebis[4-cyclohexyl], 1,2-, 1,3-, or 1,4-phenylene, 1,2-, 1,3-, or1,4-phenylenebis(methyl), biphenyl-4,4'-diyl, biphenyl-3,3'-diyl,biphenyl-3,4'-diyl, methylenebis[phenylene] , octadecane-1,2-diyl,octane-2,4-diyl, 3-butoxypropane-1,2-diyl, 1-phenylpropane-1,2-diyl,3-phenoxypropane-1,2-diyl, 3-(4-t-butylphenoxy)propane-1,2-diyl,3-(3-pentadecylphenoxy)propane-1,2-diyl, 3-allyloxypropane-1,2-diyl,1-methyl-4-isopropylidenecyclohexane-1,2-diyl,3-(alkyl(C₁₁₋₁₃)carbonyloxy)propane-1,2-diyl,4-vinylcyclohexane-1,2-diyl,2,2,6-trimethylbiciclo[3.1.1]heptane-2,3-diyl,3-(methacryloxy)propane-1,2-diyl or polybutadiene-alpha,omega-diyl.

(iii) R⁸ is 4-aza-1,7-dioxaheptane-1,4,7-triyl.

(iv) R⁸ is ##STR13## wherein Y is as previously defined, and

R²¹ is a substituted or unsubstituted aliphatic triradical of 3-20carbons, substituted or unsubstituted aryl triradical of 6-13 carbons orsubstituted or unsubstituted araliphatic triradical of 7-22 carbons,where the aliphatic, alicyclic and araliphatic triradicals may containheteroatoms nitrogen, sulfur or oxygen, with the proviso that theheteroatoms are separated from each other and Y by at least one carbonatom, or a polyester triradical having a general formula ##STR14## inwhich b is as previously defined and may be different for each of thethree repeating groups, where R²² is an aliphatic triradical of 3 to 8carbons.

Non-limiting examples of R²¹ are propane-1,2,3-triyl,pentane-1,3,5-triyl, nitrillotriethyl, --CH₂ --CH₂ --CH₂ --N(CH₂ --CH₂--)₂, 1,3,5-triazine-2,4,6-triyl, ##STR15## previously defined, and R²³is a substituted or unsubstituted aliphatic tetraradical of 4-20carbons, substituted or unsubstituted alicyclic tetraradical of 6-16carbons, substituted or unsubstituted aryl tetraradical of 6-14 carbonsor substituted or unsubstituted araliphatic tetraradical of 7-22carbons.

Non-limiting examples of R²³ are oxybis(cyclopentane-2,3-diyl),4,7,10-trioxatetradecane-1,2,13,14-tetrayl,4,9-dioxadodecane-1,2,11,12-tetrayl, butane-1,2,3,4-tetrayl, ##STR16##

(vi) R⁸ is ##STR17##

(vii) R⁸ is ##STR18## wherein ##STR19## and b is as previously defined.

(viii) R⁸ is ##STR20## wherein d is as previously defined.

(ix) ##STR21##

(x) R⁸ is ##STR22##

(xi) R⁸ is ##STR23##

(xii) R⁸ is a polymeric or copolymeric radical containing recurringunits ##STR24## wherein R²⁴ is hydrogen, alkyl of 1-4 carbons or phenyl,R²⁵ is --O--, --N(R²⁶)--, --CH₂ --O--, --C(═O)--O--CH₂ --CH(OH)--CH₂--O--, --C(═O)--O--CH₂ --CH₂ -- or --C(═O)--O--CH₂ --CH₂ --CH₂ --O--,R²⁶ is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted aryl of 6-10 carbons, substituted orunsubstituted araliphatic of 7-22 carbons or substituted orunsubstituted alicyclic of 5-12 carbons, and the symbol ˜ represents thepolymer or copolymer backbone in which the units recur.

As the anion from a carboxylic acid, A is, for example, oxalate,benzoate, formate, acetate, 4-methylbenzoate, isobutyrate, propionate,succinate, or terephthalate.

The substituents for R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²¹,R²³ and R²⁶ are independently those set forth above for R⁸.

List of Illustrative Compounds

In the following non-limiting list of illustrative compounds of thepresent invention, the N-(hindered amine)-phthalimide group appears asboth a substituent and as a parent group. The substituent nomenclatureused is N-(hindered amine)phthalimide-4-carbonyl-. When named as amolecular parent, the name follows accepted convention. 1.N-[1-(phenoxycarbonyl)-2,2,6,6-tetramethyl-4-piperidinyl]-4-(methoxycarbonyl)phthalimide2. N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(bromocarbonyl)phthalimide,hydrobromide salt 3.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(carboxy)phthalimide,p-toluenesulfonate salt 4.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4(3,5-di-t-butyl-4-hydroxybenzyloxy)carbonyl]phthalimide5.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-([2-hydroxy-3-(2H-benzotriazol-2-yl)-5-methylbenzyl]aminocarbonyl)phthalimide6.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-[5-(4-benzoyl-3-hydroxyphenoxy)-1,4-dioxo-2,3-diazapentyl]phthalimide7.N-[1-(2,3-epoxy)propyl-2,2,6,6-tetramethyl-4-piperidinyl]-4-(methoxycarbonyl)phthalimide8.N-[1-(2,3-epoxy)propyl-2,2,6,6-tetramethyl-4-piperidinyl]-4-[2,3-(epoxy)propoxycarbonyl]phthalimide9.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-([3-(methacryloxy)-2hydroxypropoxy]carbonyl)phthalimide10.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-{[3-(allyloxy)-2-hydroxypropoxy]carbonyl)phthalimide11.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-{[3-(t-butoxy)-2-hydroxypropoxy]carbonyl)phthalimide12.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-{[2-hydroxy-4-vinylcyclohexyloxy]carbonyl)phthalimide13.N-[1-(2-hydroxy-2-phenylethyl)-2,2,6,6-tetramethyl-4-piperidinyl]-4-{[2-phenyl-2-hydroxyethoxy]carbonyl)phthalimide14.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-{[2-hydroxy-2-methyl-5-(isopropylidene)cyclohexyloxy]carbonyl)phthalimide15.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-{[3-phenoxy-2-hydroxypropoxy]carbonyl)phthalimide16.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-{[3-(4-butylphenoxy)-2hydroxypropoxy]carbonyl)phthalimide17.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-{[1,5,5-trimethyl-1-hydroxybicyclo(3.1.1)heptane-2-yloxy]carbonyl)phthalimide18.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-{[3-(3-pentadecylphenoxy)-2-hydroxypropoxy]carbonyl)phthalimide19. N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-{[3-(t-alkyl(C₈-C₁₀)carbonyloxy)-2-hydroxypropoxy]carbonyl)phthalimide 20.4,4'-(4,8-dihydroxy-2,6,10-trioxa-1,11-dioxo-undecane-1,11-diyl)-bis[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide]21.1,2-di{2-hydroxy-4-oxa-4-[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide-4-carbonyl]butyl)benzene22.1,2-di{2-hydroxy-4-oxa-4-[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide-4-carbonyl]butoxy)benzene23. 4,4'-(4,14-dihydroxy-2,6,9,12,16-pentaoxa-1,17-dioxoheptadecane-1,17-diyl)-bis[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide]24.4,4'-(4,5-dihydroxy-2,7-dioxa-1,8-dioxooctane-1,8-diyl)-bis[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide]25.4,4'-(4,6-dihydroxy-4,6-dimethyl-2,8-dioxa-1,9-dioxononane-1,9-diyl)-bis[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide]26.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-{[(3,5-di(n-butylmercapto)-2,4,6-triazin-1yl]aminocarbonyl)phthalimide27.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-{[3,5-diamino-2,4,6-triazin-1-yl]aminocarbonyl)phthalimide28.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-{[3,5-dimethoxy-2,4,6-triazin-1yl]aminocarbonyl)phthalimide29.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-[(2-bromoethoxy)carbonyl]phthalimide30.6-(n-butylmercapto)-2,4-di[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide-4-carbonylamino]-1,3,5-triazine31.N-[1-(dibutylaminocarbonyl)-2,2,6,6-tetramethyl-4-piperidinyl]-4-[2-(n-butoxy)ethoxycarbonyl]phthalimide32.N-(2,2,6,6-tetramethyl-4-piperidinyl)-[1-methyl-2(ethoxycarbonyl)ethoxycarbonyl]phthalimide33.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-[6-(2,2,6,6-tetramethyl-4-piperidinyl)-2,3,6-triaza-1,4,5-trioxohexyl]phthalimide34.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-[6-(3,5-di-t-butyl-4-hydroxyphenyl)-2,3-diaza-1,4dioxohexyl]phthalimide35.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-[6-(n-hexylmercapto)-2,3-diaza-1,4dioxohexyl]phthalimide36.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-[7-(2,2,6,6-tetramethyl-4-piperidinyl)-2,3,7-triaza-1,4-dioxoheptyl]phthalimide37.1,4-di[N-(2,6-dimethyl-2,6-dipropyl-3-ethyl-4-piperidinyl)phthalimide-4-carbonyl]piperazine38.1,4-di[N-(2,2,6,6-tetramethyl-4-piperidinyl)-phthalimide-4-carbonyloxy]benzene39.N-(1-[(butoxycarbonyl)methyl]-2,2,6,6-tetramethyl-4-piperidinyl)-4-(butoxycarbonyl)phthalimide40.2,2-di(4-[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide-4-carbonyloxy]phenyl}propane41.4,4'-(4-hydroxy-2,6-dioxa-1,7-dioxoheptane-1,7-diyl)-bis[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide]42.4,4'-(2,5,8-trioxa-1,9-dioxononane-1,9-diyl)bis[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide]43.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-{[3(trimethoxysilyl)propyl]aminocarbonyl)phthalimide44.N-(1-benzyl-2,2,6,6-tetramethyl-4-piperidinyl)-4-{[2-(dimethylamino)ethyl]aminocarbonyl}phthalimide45.1,4-di[N-(2,6-diethyl-2,6-dimethyl-3-methyl-4-piperidinyl)phthalimide-4-carbonylamino]benzene46.4,4'-[4,4-di(hydroxymethyl)-2,6-dioxa-1,7-dioxoheptane-1,7-diyl)]-bis[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide]47.4,4'-(4,4-di{[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide-4-carbonyloxy]methyl)-2,6-dioxa-1,7-dioxoheptane-1,7-diyl}-bis[N-2,2,6,6-tetramethyl-4-piperidinyl)phthalimide]48. N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-carboxyphthalimide, esterwith poly(caprolactone)-triol, 3:1 49.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-carboxyphthalimide, ester withpoly(propyleneoxide)-diol, 2:1 50.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-carboxyphthalimide, product withepoxy resin (Bisphenol-A/epichlorohydrin) 51.1,4-di{[N-(2,2,6,6-tetramethyl-4-piperidinyl)-phthalimide-4-carbonyloxy]methyl)cyclohexane52.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-{[2-(4-benzoyl-3hydroxyphenoxy)ethoxy}carbonyl]phthalimde53.7-[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide-4-carbonyloxy]-3-([N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide-4-carbonyloxy]methyl)tricyclo(5.2.1.0¹,5)decane54.4,4'-(4-[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide-4-carbonylmercapto]-2,6-dioxa-1,7-dioxoheptane-1,7-diyl)-bis[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide]55.1,3-di[N-(2,2,6,6-tetramethyl-4-piperidinyl)-phthalimide-4-carbonylamino]-4-{6-[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide-4carbonyl]-5-oxa-1-thiapentyl)benzene56. N-(1,2,2,6,6-pentamethyl-4-piperidinyl)-4{[(3-benzoyloxy)phenoxy]carbonyl)phthalimide 57.N-[1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4piperidinyl]-4-([2-(acryloyloxy)ethoxy]carbonyl)phthalimide58.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-[(2aminoethyl)aminocarbonyl]phthalimide59. methyl methacrylate/glycidylmethacrylate/N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-{[3-(methacryloyloxy)-2-hydroxypropoxy]carbonyl)phthalimideterpolymer 60.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-carboxyphthalimide, ester withpoly[oxycarbonyloxy-1,4-phenylene(1-methylethylidene)-1,4-phenylene],2:1 61.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(2-hydroxypropoxycarbonyl)phthalimide62.N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-([2-(3,3-diphenyl-2-cyanoacryloyloxy)ethoxy]carbonyl)phthalimide63.2-(N-[methoxymethyl]-N-[n-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide-4carbonyloxymethyl]amino)-4,6-di[N,N-di(methoxymethyl)amino]-1,3,5-triazine64.4,4'-(2,7-dioxa-1,8-dioxo-4-octene-1,8-diyl)bis[N-(1-benzoyl-2,2,6,6-tetramethyl-4-piperidinyl)phthalimide]65.2,4-di[N-(2,2,6,6-tetramethyl-4-piperidinyl)-phthalimide-4-carbonylamino]-1-{2-[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide-4-carbonyl-oxy]ethoxy)benzene66.4,4'-(ethane-1,2-diyl)bis(N-[1[(cyclohexyloxycarbonyl)methyl]-2,2,6,6-tetramethyl-4-piperidinyl)phthalimide]67.tri([N-(2,2,6,6-tetramethyl-4-piperidinyl)-phthalimide-4-carbonyloxy]ethyl)amine68.4-(2-phenoxyethoxy)carbonyl-N-[1-(2-acetoxyethyl)-2,2,6,6-tetramethyl-4piperidinyl]phthalimide69.alpha,omega-di[N-(2,6-diethyl-2,6-dimethyl-3-methyl-4-piperidinyl)phthalimide-4-carbonyloxy]polybutadiene70.N-(1-butyl-2,2,6,6-tetramethyl-4-piperidinyl)-4-(N-methyl-N-phenylaminocarbonyl)phthalimide,trihydrogen phosphate salt.

Utility

The novel stabilizers of this invention are effective additives for thestabilization of polymeric compositions which are normally subject tothermal, oxidative or actinic light degradation. At times it may bebeneficial to add extraneous additives which will act as synergists withthe hindered amine light stabilizing group.

Thus, another aspect of the present invention relates to a process ofstabilizing a synthetic or natural polymer composition against thedegradative effects of heat or light by mixing with the polymercomposition a compound of general formula I in an amount effective tostabilize the polymer composition against the degradative effects ofheat or light.

Yet another aspect of this invention concerns a polymeric compositionstabilized against the degradative effects of heat or light comprising asynthetic or natural polymer mixed with a compound of general formula Iin an amount effective to stabilize the polymer against the degradativeeffects of heat or light.

The novel stabilizers of this invention can be blended with variouspolymeric compositions in high concentrations to form masterbatcheswhich can then be blended with additional polymer either of the same ordifferent type.

The amount of stabilizer used to stabilize the polymeric compositionwill depend on the particular polymer system to be stabilized, thedegree of stabilization desired and the optional presence of otherstabilizers in the composition. Normally it is advisable to have about0.01 to about 5% by weight of the 2,2,6,6,-tetraalkylpiperidine moietyof the compound of this invention present in the polymeric composition.An advantageous range is from about 0.05 to about 2% by weight of the2,2,6,6-tetraalkylpiperidine portion of the molecule in the finalcomposition. In most cases about 0.1% to about 1% by weight issufficient.

Non-limiting examples of polymers and copolymers which may be stabilizedby the compounds of the present invention include:

1. Polyolefins, such as high, low and linear low density polyethylenes,which may be optionally crosslinked, polypropylene, polyisobutylene,poly(methylbutene-1), polyacetylene and, in general, polyolefins derivedfrom monomers having from 2 to about 10 carbon atoms, and mixturesthereof.

2. Polyolefins derived from diolefins, such as polybutadiene andpolyisoprene.

3. Copolymers of monoolefins or diolefins, such as ethylene-propylene,propylene-butene-1, propylene-isobutylene and ethylene-butene-1copolymer.

4. Terpolymers of ethylene and propylene with dienes (EPDM), such asbutadiene, hexadiene, dicyclopentadiene and ethylidene norbornene.

5. Copolymers of alpha-olefins with acrylic acid or methacrylic acids ortheir derivatives, such as ethylene-acrylic acid, ethylene-methacrylicacid and ethylene-ethyl acrylate copolymers.

6. Styrenic polymers, such as polystyrene (PS) andpoly(p-methylstyrene).

7. Styrenic copolymers and terpolymers, such as styrene-butadiene (SBR),styrene-allyl alcohol and styrene-acrylonitrile (SAN),styrene-acrylonitrile-methacrylate terpolymer, styrene-butadiene-styreneblock copolymers (SBS), rubber modified styrenics such asstyrene-acrylonitrile copolymers modified with acrylic ester polymer(ASA), graft copolymers of styrene on rubbers, such as polybutadiene(HIPS), polyisoprene or styrene-butadiene-styrene block copolymers,graft copolymers of styrene-acrylonitrile on rubbers, such as butadiene(ABS), polyisoprene or styrene-butadiene-styrene block copolymers, graftcopolymers of styrene-methyl methacrylate on rubbers, such aspolybutadiene (MBS), butadiene-styrene radial block copolymers (e.g. KRO3™ of Phillips Petroleum Co.), selectively hydrogenatedbutadiene-styrene block copolymers (e.g. Kraton G™ from Shell ChemicalCo.), and mixtures thereof.

8. Polymers and copolymers derived from halogen-containing vinylmonomers, such as poly (vinyl chloride), poly (vinyl fluoride), poly(vinylidene chloride), poly (vinylidene fluoride), poly(tetrafluoroethylene) (PTFE), vinyl chloride-vinyl acetate copolymers,vinylidene chloride-vinyl acetate copolymers andethylenetetrafluoroethylene copolymers.

9. Halogenated rubbers, such as chlorinated and/or brominated butylrubbers, such as chlorinated and fluoroelastomers.

10. Polymers and copolymers derived from alpha, beta-unsaturated acids,anhydrides, ester, amides and nitriles or combinations thereof, such aspolymers or copolymers of acrylic and methacrylic acids, alkyl and/orglycidyl acrylates and methacrylates, acrylamide and methacrylamide,acrylonitrile, maleic anhydride, maleimide, the various anhydridecontaining polymers and copolymers described in this disclosure,copolymers of the polymers set forth in this paragraph and variousblends and mixtures thereof, as well as rubber modified versions of thepolymers and copolymers set forth in this paragraph.

11. Polymers and copolymers derived from unsaturated alcohols or theiracylated derivatives, such as poly (vinyl alcohol ), poly (vinylacetate), poly (vinyl stearate), poly(vinyl benzoate), poly(vinylmaleate), poly(vinyl butyral), poly(allyl phthalate), poly(allyldiethylene glycol carbonate) (ADC), ethylene-vinyl acetate copolymer andethylenevinyl alcohol copolymers.

12. Polymers and copolymers derived from unsaturated amines, such aspoly(allyl melamine).

13. Polymers and copolymers derived from epoxides, such as polyethyleneoxide, polypropylene oxide and copolymers thereof, as well as polymersderived from bis-glycidyl ethers.

14. Poly (phenylene oxides), poly(phenylene ethers) and modificationsthereof containing grafted polystyrene or rubbers, as well as theirvarious blends with polystyrene, rubber modified polystyrenes or nylon.

15. Polycarbonates and especially the aromatic polycarbonates, such asthose derived from phosgene and bisphenols such as bisphenol-A,tetrabromobisphenol-A and tetramethylbisphenol-A.

16. Polyester derived from dicarboxylic acids and diols and/orhydroxycarboxylic acids or their corresponding lactones, such aspolyalkylene phthalates (e.g. polyethylene terephthalate (PET),polybutylene terephthalate (PBT) and poly(1,4-dimethylcyclohexaneterephthalate) or copolymers thereof) and polylactones, such aspolycaprolactone.

17. Polyarylates derived from bisphenols (e.g. bisphenol-A) and variousaromatic acids, such as isophthalic and terephthalic acids or mixturesthereof.

18. Aromatic copolyestercarbonates having carbonate, as well as esterlinkages present in the backbone of the polymers, such as those derivedfrom bisphenols, iso- and terephthaloyl chlorides and phosgene.

19. Polyurethanes and polyureas.

20. Polyacetals, such as polyoxymethylenes and polyoxymethylenes whichcontain ethylene oxide as a comonomer.

21. Polysulfones, polyethersulfones and polyimidesulfones.

22. Polyamides and copolyamides which are derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactones, such as the following nylons: 6, 6/6, 6/10, 11and 12.

23. Polyimides, polyetherimides, polyamideimides and copolyetheresters.

24. Crosslinked polymers which are derived from aldehydes on the onehand and from phenols, ureas and melamine on the other hand, such asphenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.

25. Alkyl resins, such as glycerolphthalic acid resins and mixturesthereof with melamine-formaldehyde resins.

26. Unsaturated polyester resins which are derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcohols,as well as from vinyl compounds (crosslinking agents) and alsohalogen-containing, flame resistant modifications thereof.

27. Natural polymers, such as cellulose, natural rubber, as well as thechemically modified homologous derivatives thereof, such as celluloseacetates, cellulose propionate, cellulose butyrate and the celluloseethers, such as methyl and ethyl cellulose.

In addition, the stabilizers of this invention may be used to stabilizevarious combinations or blends of the above polymers or copolymers. Theyare particularly useful in the stabilization of polyolefins, acryliccoatings, styrenics, rubber modified styrenics, poly(phenylene oxides)and their various blends with styrenics, rubber-modified styrenics ornylon.

The hindered amine light stabilizers of this invention can be usedtogether with other additives to further enhance the properties of thefinished polymer. Examples of other additives that can be used inconjunction with the stabilizers of this invention include otherantioxidants, such as alkylated monophenols, alkylated hydroquinones,hydroxylated thiodiphenyl ethers, alkylidene-bis-phenols, hinderedphenolic benzyl compounds, acylamino-phenols, esters of3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid, esters of3-(5-t-butyl-4-hydroxy-3-methylphenyl)propionic acid,3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid amides; other UVabsorbers and light stabilizers, such as2-(2'-hydroxyphenyl)-2H-benzotriazoles, 2-hydroxybenzophenones,benzylidene malonate esters, esters of substituted or unsubstitutedbenzoic acids, diphenyl acrylates, nickel chelates, oxalic aciddiamides, other hindered amine light stabilizers; other additives suchas metal deactivators, phosphites and phosphonites, peroxidedecomposers, fillers and reinforcing agents, plasticizers, lubricants,corrosion and rust inhibitors, emulsifiers, mold release agents, carbonblack, pigments, fluorescent brighteners, both organic and inorganicflame retardants and non-dripping agents, melt flow improvers andantistatic agents. Numerous examples of suitable additives of the abovetype are given in Canadian Patent No. 1,190,038.

The polymeric derivatives are particularly attractive, offering enhancedcompatibility and non-fugitivity when used to stabilize polymercompositions in which they are incorporated.

Preparative Methods

The preparation of the compounds of this invention involves theformation of an imide by reaction of trimellitic acid derivatives and anamino-substituted hindered amine light stabilizer of formula ##STR25##in which R¹ and X are as previously defined. Syntheses of such hinderedamine light stabilizers are well-known in the art.

Trimellitic acid derivatives which can be used have a general formula##STR26## where R⁸ and s are as previously defined and R²⁷ and R²⁸ areindependently lower alkyl of 1-8 carbons, phenyl or benzyl. The imideformed is formula I.

All the compounds of this invention may be considered as derivatives ofthe following general formula II which is shown without optionalsubstitution to illustrate the addition product (imide) from twocompounds: trimellitic anhydride and2,2,6,6-tetrasubstituted-4-aminopiperidine derivative shown above:##STR27##

This compound, which contains both carboxylic acid and amine base,exists as an inner salt (iminio carboxylate). This is not necessarilytrue for all possible derivatives and in more general form the additionproduct becomes ##STR28## wherein R¹, R⁸, s and X are as previouslydefined.

Depending on the definition of R⁸, R² and R³ additional reaction may benecessary to prepare other compounds of this invention. In this case,additional starting materials can be used.

Other starting materials are commercially available amines, alcohols,mercaptans, alkyl halides, amides, anhydrides, acyl halides,chloroformates, epoxides, isocyanates and esters.

Some of the starting materials which can be used in the preparation ofthis invention are commercially available polymeric materials such

1. K-FLEX® polyester polyols, available from King Industries SpecialtyChemicals.

2. FOMREZ® 53, a hydroxy terminated saturated polyester available fromWhitco Chemical Organics Division.

3. JEFFAMINE® polyoxyalkyleneamines, primary amine terminated polyethersavailable as monoamines, diamines and triamines, available from TexacoChemical Company.

4. POLYWAX®, liquid, hydroxy terminated polymers of butadiene, availablefrom ARCO Chemical Company.

5. PERMPAL®, polythioether diols available from Products Research &Chemical Corporation.

6. POLYWAX® OH alcohols, primary linear polymeric alcohols with a fullysaturated hydrocarbon backbone, available from Petrolite Corporation.

7. HYCAR® reactive liquid polymers, hydroxy terminatedbutadiene/acrylonitrile copolymers available from Goodrich ChemicalCompany, Chemical Group.

8. RJ-100® and RJ-101®, styrene/allyl alcohol copolymers available fromMonsanto Company.

9. Saytech Experimental Polyol 42-77, a brominated polyester polyolavailable from Saytech Inc.

10. MAZER™ SFR Reactive Silicone fluids, which are reactivePolydimethylsiloxanes with terminal hydroxy sites, available from MAZERChemicals, Inc.

11. TONE™ Polyols, diols and triols based on polycaprolactone, availablefrom Union Carbide Corporation.

12. DURACARB ® hydroxy terminated aliphatic polycarbonates, availablefrom PPG Industries.

13. Epoxy resins, such as those derived from Bisphenol-A andepichlorohydrin which have 1 or more residual epoxy groups attached tothe polymer.

14. NIAX® polyether polyols available from Union Carbide Corporation.

15. CARBOWAX® polyethylene glycols and methoxy polyethylene glycolsavailable from Union Carbide Corporation.

16. Any of a number of surfactants with a free hydroxy group, such asTRITON® X-100, a product of Rohm & Haas company.

In addition, there are many other polymeric derivatives that can bemade. The HALS moiety can be attached to any polymer with reactivefunctionality similar to those discussed above. Particularly useful arepolymers containing residues of monomers such as vinyl alcohol,2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, hydroxypropyl(meth)acrylate. Additional commercially available polymers have hydroxygroups along the polymer chain or as end groups. Examples of these typesof polymers are Bisphenol-A polycarbonate, polyphenylene oxide,hydroxypropyl cellulose and hydroxypropyl methyl cellulose.

Inner salt II is a versatile intermediate for further elaboration intoadditional compositions of this invention. In addition to thepreparation methods set forth in detail in the examples, another methodof preparing inner salt II would involve the reaction of theamino-substituted piperidine with an appropriate diester, ester-acid,amide-ester, ester-acid chloride or diacid dichloride. Such preparationsare described in the chemical literature.

Esterification of inner salt II may be accomplished in many ways.Alkylation by a reactive alkyl chloride, bromide or iodide can be doneunder neutral or alkaline conditions in a solvent, such as aromatichydrocarbons, chlorinated alkanes, ketones (such as acetone, methylethyl ketone), ethers (such as methyl t-butyl ether, tetrahydrofuran),amides (such as N-methylpyrrolidone, N,N-dialkylformamide), sulfolane ordimethylsulfoxide, alone or in combination. Esterification by epoxidesis carried out in a similar manner. The concentration of reactants inthe solvent is not critical as long as both reactants are at leastpartially soluble. The preferred solvent is dimethylformamide or solventmixtures in which it is present. The mole ratio of inner salt II toalkylating agent can range from about 1:1 to about 1:10 and varies basedon the desired product. If the hindered amine is not tertiary (X═--NH--or --NH₂.sup.⊕ --) before this reaction, the alkylation may include bothcarboxyl and amine substitution. This can be controlled viastoichiometry to favor only alkylation of carboxyl (1 equivalentalkylating agent) to alkylation of both carboxyl and amine (twoequivalents or more). The alkylation can be done in the presence of anacid acceptor, such as a tertiary amine, or an inorganic base, such asan alkali metal carbonate, bicarbonate or hydroxide. The added base isrequired to liberate the amine if it is participating in a salt. Timeand temperature conditions are such that the reaction proceeds at areasonable rate. Typical conditions would be ambient temperature up tothe refluxing temperature of the chosen solvent (up to about 200° C.)and a reaction duration of about 1 to about 72 hours. The preferredtemperature range is room temperature up to about 150° C.

Also beneficial in certain instances is the inclusion of a phasetransfer catalyst (PTC) to enable the reaction either by increasing itsrate or by aiding dissolution of the starting materials. The amount ofPTC is generally about 0.01 to about 0.5 mole % based on inner salt II,preferably about 0.05 to about 0.2 mole %. An example of a PTC would bea tetraalkylammonium halide. Many such compounds are commerciallyavailable.

The acid halide of inner salt II is a versatile intermediate which isprepared by contacting the free acid or an alkali metal salt with areactive halogenating agent, such as thionyl chloride, thionyl bromide,phosphorus trichloride or tribromide, phosphorus pentachloride,phosphorous pentabromide, phosphorus oxychloride or other knownhalogenating agents. This reaction is best done using excesshalogenating agent as solvent, although inert solvents, such as aromatichydrocarbons or halogenated alkanes may also be used. The formationreaction can be done at a variety of temperatures for various timeperiods depending upon the reactivity of the halogenating agent and theacid derivative. Temperatures from ambient up to refluxing solvent (upto about 150° C.) may be employed. The reaction is continued untilconversion is complete, generally about 1 to about 24 hours or longer.

The product of reaction is the ammonium salt of the acid halide and thisoften precipitates from the reaction mixture as formed. In thisinstance, the product is conveniently isolated by filtration from thereaction mixture. If the product does not precipitate, the solvent andexcess halogenating agent is stripped away from the product using commonmethods. This intermediate must be protected from moisture whichhydrolyzes it back to the acid. A preferred method is described in theexamples section.

The monoester or polyester, thioester and amide derivatives (or mixturesthereof) can be prepared via the acid halide intermediate, by reactionwith the appropriate monoalcohol or polyalcohol, amine or mercaptan (ormixture). This acylation reaction is best carried out in solvent with anacid acceptor to remove the halogen acid as formed and to free the acidhalide ammonium salt. An excess of the compound being acylated isdesirable, especially for monoacylated compositions. In the case of themonoamine or polyamine starting materials, excess amine can serve as thehalogen acceptor. In the case of the monoalcohol or polyalcohol ormercaptan starting materials, an additional base, either a tertiaryamine or an inorganic base, such as an alkali metal carbonate,bicarbonate or hydroxide, can be used. The mole ratio of alcohol,mercaptan and amine groups to the acid halide is calculated based on theequivalents of reactive hydroxy, mercapto and amino groups available andthe desired degree of substitution, providing one equivalent of acidhalide for each equivalent of hydroxy, mercaptan or amine to beacylated. For a heterogeneous base, a PTC as described above can bebeneficial. The acylation reaction may be carried out over a wide rangeof temperatures, particularly ambient temperature up to the refluxingtemperature of the reaction medium (up to about 200° C.). The durationof the reaction is chosen based on product and the rate of conversion ofstarting material to product and can vary from about 1 to about 72hours.

The hydrazide (General Formula I where R⁸ is NHNH₂) may be prepared byreacting the esters (where R⁸ is R¹¹ --O--), halides (where R⁸ is chloroor bromo) and amides (where R⁸ is --N(R¹¹)(R¹²) with hydrazine orhydrazine hydrate. Typically, the ester used is dissolved in a polarsolvent and converted to the desired hydrazide by stirring with anequivalent amount or slight excess of hydrazine or hydrazine hydrate.The reaction may go at room temperature or may require heating.Preferably the hydrazinolysis reaction is carried out on a lower alkylester in methanol or ethanol. Substituted hydrazides can be prepared byreacting the esters with substituted hydrazines.

Other derivatives of the parent hydrazide are hydrazones, carbamoyl andthiocarbamoyl derivatives which may be prepared by reacting thehydrazides with ketones, aldehydes, isocyanates, disocyanates,isothiocyanates or diisothiocyanates. Such reactions are well known inthe art and can occur under a wide variety of temperatures, times,solvents and concentrations. Generally, a mole ratio of about 0.9 toabout 1.0 to about 1.1 to about 1.0 of the hydrazide to themonofunctional coreactant is employed. If the coreactant isdifunctional, then a mole ration of about 1.8 to about 2.0 to about 1.1to about 1.0 of the hydrazide to the difunctional coreactant isemployed. If the coreactant is a compound that can easily be removedfrom the product, e.g. acetone or methyl ethyl ketone, lower mole ratiosmay be desirable. In fact, it may be desirable to use the coreactant asthe solvent.

The acyl derivatives of the hydrazide may be prepared by reacting theester (as described above) with acid hydrazides in refluxing alcohol(i.e., methanol).

The alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl andaralkoxycarbonyl derivatives of the hydrazide may be prepared byreacting the ester (as described above) with the corresponding alkyl,cycloalkyl, aryl or aralkyl carbazates in refluxing alcohol (i.e.,methanol). Alternately, these derivatives may be prepared by reactingthe hydrazide with a disubstituted carbonate or substituted haloformate.When a haloformate is used, an additional base (inorganic or amine) maybe used to react with the halogen acid formed.

The alkyl derivatives of the hydrazide may also be prepared by reactingthe hydrazides with epoxides. The reactions are generally carried outneat or in a minimum amount of a high boiling solvent. Reactiongenerally occurs quite readily at about 140° C. to about 150° C. Thehydrazide group reacts with two equivalents of epoxide. The ratio of theunsubstituted hydrazide to the monoalkylated and dialkylated products isdependent upon the mole ratio of epoxide to hydrazide, the temperatureand the concentration if the reaction is run in a solvent.

Polymeric derivatives can be prepared by five main methods: acylation ofpolymers bearing reactive hydroxy, amino, mercapto or epoxy groups;(co)polymerization of derivatives of the acid, as for example,2-(methacryloyloxy)ethyl ester or the allyl ester; graft polymerizationof the same monomeric HALS onto a polymer backbone; functionalization ofcondensation polymers through use of a molecular weight regulator; andattachment of a suitably structured HALS derivative through its use as achain transfer agent.

The acylation is conducted as described previously.

The polymerization of monomeric derivatives either alone or with othermonomers is performed using any of the well known methods employed inthe art for copolymerizing ethylenic or vinyl aromatic monomers with themonomer functionality incorporated into the HALS-imide. Description ofsuch methods are described in Kirk-Othmer Encyclopedia of ChemicalTechnology, 3rd Ed., Vol 18, "Polymerization Mechanisms and Processes",pp. 720-744. In addition, 5 to 40 percent by weight of one of the knownelastomers may be incorporated into the copolymer by copolymerizing themonomers in the presence of the rubber. Preferably, the elastomers areincorporated into the monomer mixture prior to polymerization using, forexample, the methods of U.S. Pat. Nos. 4,097,551 or 4,486,570. Preferredrubbers are diene rubbers, such as homopolymers of conjugated dienes,such as butadiene, isoprene, chloroprene or piperylene and copolymers ofsuch dienes with up to 50 mole percent of one or more copolymerizablemono-ethyleneically unsaturated monomers, such as styrene, substitutedstyrenes, acrylonitrile, methacrylonitrile or isobutylene.

The polymeric derivatives can also be prepared by grafting the monomericHALS-imide onto a polymer. The polymer may be high or low densitypolyethylene, a polypropylene or a copolymer of alpha olefins having upto about six carbons, or any other polymer having a labile hydrogen onthe polymer backbone. Examples of such copolymers are ethylene-butene-1,ethylene-propylene and propylene-butene-1 copolymers. The method ofgrafting the HALS monomer onto the polymers is similar to the methodsknown in the art for such reactions. Briefly, the preparation comprisestreating the polymer with a free radical initiator which generates freeradicals on the polymer. The free radical sites on the polymer can thenadd on the unsaturated HALS-monomer. Active radical sites on the polymerbackbone can also be induced by subjecting the polymer to the action ofhigh energy ionizing radiation, such as gamma rays, X-rays or high speedelectrons or by simply milling the polymer in the presence of air.Examples of applicable methods are described in U.S. Pat. Nos. 3,483,276and 4,506,056.

The free acid group in the HALS derivative can be used to control themolecular weight of polymers prepared by condensation polymerization,such as polyamides, polycarbonates and polyesters. The technique ofadding a monobasic acid for molecular weight control is well known inthe art. In this process, the monobasic acid (in this case the HALSderivative) becomes attached to the polymer molecule as an endgroup.

A HALS derivative with a labile hydrogen can be introduced into apolymerization mixture as a chain transfer agent. In this capacity, theHALS would also be incorporated as a polymer end group. The mechanismhere comprises termination of a growing polymer chain by donation of thelabile hydrogen and initiation of another polymer chain from the activesite thus formed on the HALS molecule. Such a technique is known in theart.

The invention will now be described in more detail with reference to thefollowing specific, non-limiting examples. In the following exampleswhere appropriate, analytical data is included to further define theproducts. All melting points are uncorrected. Spectral data was obtainedusing common practices. All NMR spectra were recorded in chloroform-d(unless otherwise specified) relative to tetramethylsilane (0.0 ppm).

EXAMPLE 1 Preparation ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-4-carboxyphthalimide, internalsalt

Into a 2 liter round bottom flask equipped with a mechanical stirrer,nitrogen atmosphere and thermometer were placed 149.5 g (0.75 mol)trimellitic anhydride and 500 ml of acetic acid. This mixture was cooledand stirred while 34.1 g (0.85 mol) sodium hydroxide (solid) were added(exothermic). After addition of base, cooling was discontinued and themixture was stirred while 128.9 g (0.82 mol) of4-amino-2,2,6,6-tetramethylpiperidine were slowly added, using anadditional 250 ml of acetic acid to rinse the amine into the flask. Thisaddition was also exothermic and the heat evolved was used to warm thereaction mixture to about 90° C. After complete addition, the reactionwas refluxed for 2 hours. The hot reaction mixture was poured onto 1000g ice in a beaker and the mixture stirred until the ice melted. Thesolid product was isolated by filtration and slurried twice with 700 mlportions of acetone. A significant static charge complicates handling ofthe product. The white product weighed 216.2 g (87.3% theoretical). Theinfrared spectrum (KBr pellet) of this compound showed the carbonylabsorptions for the imide (1700 cm⁻¹) and the carboxylate (1620 cm⁻¹).The piperidinium salt N--H was indicated by a broad band 2000-3000 cm⁻¹.During heating at 20° C./minute in the differential scanningcalorimeter, the salt began decomposing at about 350° C.

EXAMPLE 2 Preparation ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(chlorocarbonyl)phthalimide,hydrochloride salt

Into a dry 500 ml round bottom flask equipped with a magnetic stirrer,reflux condenser and nitrogen atmosphere were placed 175 g (1.5 mol)thionyl chloride. 69.9 g (0.21 mol)N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-carboxyphthalimide were added insmall portions over a 45 minute period. The resulting mixture wasrefluxed for an hour before stirring became difficult (due toprecipitated product) and 25 g (0.21 mol) thionyl chloride was added toalleviate this problem. The mixture was refluxed for three additionalhours. The reaction mixture was cooled to room temperature and dilutedwith 600 ml methyl t-butyl ether. The solid product was isolated byfiltration and washed on the funnel with three 100 ml portions of ether.Final removal of solvent was accomplished under high vacuum, giving 76.7g white crystals. By analysis for hydrolyzable chloride, the sample wasdetermined to be 99+% assay. The yield was 94.8%. The infrared spectrum(KBr pellet) of this compound showed the carbonyl absorptions for theimide (1705 cm⁻¹) and the carbonyl chloride (1750 cm⁻).

EXAMPLE 3 Preparation ofN-(2,2,2,6-tetramethyl-4-piperidinyl)-4-(aminocarbonyl)phthalimide

Into a 125 ml Erleruneyer flask equipped with a thermometer were placed50 ml concentrated aqueous ammonium hydroxide. The acid chloride ofExample 2 (5.0 g, 0.013 mol) was added and the mixture stirred for 30minutes. The solid product was collected by filtration and washed withseveral portions of water. The product was dried briefly on the funnel,then dissolved in hot methanol and filtered (hot). Upon cooling theproduct crystallized. The crystallized material was isolated byfiltration, yielding 1.1 g of white crystals (melting at 189°-194° C.).Reduction of the crystallization solvent produced a second crop ofproduct, 0.25 g (melting at 189°-200° C.). The infrared spectrum (KBrpellet) of the product showed an intense broad carbonyl for both theamide and the imide at 1680-1720 cm⁻¹.

EXAMPLE 4 Preparation ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(ethox-ycarbonyl)phthalimide

Into a 125 ml reaction flask equipped with magnetic stirrer,thermometer, addition funnel and nitrogen atmosphere were placed 5.0 g(0,013 mol) of acid chloride from Example 2 and 25 ml ethanol. Theaddition funnel was charged with 15 ml ethanol and 2.8 g (0.028 mol)triethylamine. The reaction mixture was stirred as the base was addedover a 5 minute period accompanied by a 10° C. exotherm. The mixture wasstirred at ambient temperature for 2 hours, during which time suspendedsolid slowly dissolved. The reaction mixture was stripped of solventusing an aspirator vacuum. The solid was taken up in 100 ml toluene in aseparatory funnel and washed with 50 ml saturated sodium bicarbonate andthree 50 ml portions of water. The toluene solution was dried withanhydrous magnesium sulfate and stripped of solvent to yield 4.0 g ofproduct. This material was recrystallized from 95% ethanol, producing2.6 g of white crystals (melting at 115°14 121° C.). The infraredspectrum (KBr pellet) of the product showed a doublet carbonyl withabsorbance maxima of 1705 cm⁻¹ (imide) and 1710 cm⁻¹ (ester). The NMRspectrum indicated the presence of the ethyl group (4.4 ppm, quartet,2H; 1.4 ppm, triplet) and the aromatic ring (7.8-8.0 ppm, doublet, 1H;8.3-8.5, multiplet, 2H) and the HALS group [4.5-4.8 ppm, multiplet, 1H;1.0-2.3 ppm several multiplets including two singlets (1.2 and 1.3ppm)].

EXAMPLE 5 Preparation ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(2,2,6,6-tetramethyl-4-piperidinyloxycarbonyl)phthalimide

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed 5.0 g (0.013mol) of the acid chloride of Example 2 and 50 ml of 2% dimethylformamidein methylene chloride. This mixture was stirred during the addition of2.1 g (0.013 mol) 2,2,6,6-tetramethyl-4-piperidinol and 2.8 g (0.028mol) triethylamine. The reaction was then refluxed for 3 hours. Themixture was cooled and transferred to a separatory funnel with 100 mlmethylene chloride, 25 ml water and 50 ml 5% sodium hydroxide. Themixture was shaken, allowed to separate and the organic phase drawn off.The aqueous phase (and interfacial solid) was extracted with anadditional 25 ml solvent. The combined organic solutions were dried withanhydrous magnesium sulfate and the solvent stripped using aspiratorvacuum. The product was 4.1 g of slightly yellow crystals (melting at196°-200° C.). The infrared spectrum (chloroform) showed the carbonylabsorption at 1705 cm⁻¹ (imide and ester). The NMR Spectrum showed theanticipated aromatic ring (7.7-7.9 ppm, doublet, 1H; 8.3-8.5, multiplet,2H) and two HALS groups [5.2-5.7 ppm, multiplet, 1H; 4.4-4.9 ppm,multiplet, 1H; 1.0-2.3 ppm, several multiplets including two singlets(1.2 and 1.3 ppm)]. The UV spectrum showed an absorbance maximum (THF)at 296 nm, molar absorptivity 300.

EXAMPLE 6 Preparation ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-4-[(2-ethylhexyloxy)carbonyl]phthalimide

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed 5.0 g (0.013mol) of the acid chloride of Example 2, 1.7 g (0.013 mol) 2-ethylhexanoland 50 ml of 2% dimethylformamide in methylene chloride. This mixturewas stirred during the addition of 2.8 g (0.028 mol) triethylamine in 5ml methylene chloride. This addition produced an exotherm of about 10°C. The reaction was then refluxed for 1 hour. The mixture was cooled andtransferred to a separatory funnel with 100 ml methylene chloride and250 ml water. The ensuing emulsion was filtered, put back in the funneland the phases separated. The organic phase was extracted with 50 mlwater and 50 ml 5% sodium bicarbonate. The organic solution was driedwith anhydrous magnesium sulfate and the solvent stripped usingaspirator and high vacuum. Liquid chromatographic analysis of the whitesolid product indicated the presence of two components. The material wasredissolved in methylene chloride and extracted with two 50 ml portionsof 5% sodium hydroxide. The organic solution was again dried andstripped and the residue recrystallized from 80/20 ethanol/water. Afterisolation and drying, 1.5 g of slightly yellow product were obtained(melting 129°-131° C.). The infrared spectrum (KBr pellet) showed thecarbonyl absorption at 1720 cm⁻¹ (imide and ester). The NMR spectrumshowed the anticipated aromatic ring (7.7-7.9 ppm, doublet, 1H; 8.2-8.5,multiplet, 2H) and the 2-ethylhexyl and HALS groups [4.4-4.9 ppm,multiplet, 1H; 4.2-4.3 ppm, doublet, 1H; 0.7-2.3 ppm, several multipletsincluding two singlets (1.2 and 1.3 ppm)].

EXAMPLE 7 Preparation ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(dodecylaminocarbonyl)phthalimide

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed 2.4 g (0.013mol) dodecylamine and 40 ml of 2% dimethylformamide in methylenechloride. This mixture was stirred during the addition of 5.0 g (0.013mol) of the acid chloride of Example 2 accompanied by an 8° C. exotherm.The reaction mixture was cooled to ambient temperature and 2.8 g (0.028mol) triethylamine was added, producing an exotherm of about 10° C. Thereaction was allowed to stir at room temperature for 30 minutes thentransferred to a separatory funnel with 50 ml methylene chloride and 50ml water. The phases were separated and the organic phase was furtherextracted with three 50 ml portions of water. Additional solvent, 50 ml,was added and the organic solution washed with two 50 ml portions of 5%sodium hydroxide. The organic solution was dried with anhydrousmagnesium sulfate and the solvent stripped using aspirator and highvacuum systems. The product was 6.1 g (98% of theory) of a yellowsemi-solid which upon standing became a solid (melting at 42°-45° C.).The infrared spectrum (chloroform) showed two carbonyl absorptions at1720 cm⁻¹ (imide) and 1660 cm⁻¹ (amide). The NMR spectrum showed theanticipated aromatic ring (7.7-7.9 ppm, doublet, 1H; 8.1-8.3, multiplet,2H), the amide N--H (6.4-6.8 ppm, multiplet, 1H), the amide methylene(3.2-3.7 ppm, multiplet, 2H) and HALS group and amide residue [4.4-4.9ppm, multiplet, 1H; 0.7-2.3 ppm, several multiplets].

EXAMPLE 8 Preparation ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(dibutylaminocarbonyl)phthalimide

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed 5.0 g (0.013mol) of acid chloride of Example 2 and 50 ml of 2% dimethylformamide inmethylene chloride. This mixture was stirred during the addition of 1.7g (0.013 mol) of di-n-butylamine accompanied by a 10° C. exotherm. Thereaction mixture was cooled to ambient temperature and 2.8 g (0.028 mol)triethylamine were added, producing an exotherm of about 10° C. Thereaction was cooled to room temperature and allowed to stir for 1 hour,then transferred to a separatory funnel with 50 ml methylene chlorideand 50 ml water. Upon shaking, an emulsion formed which was broken bythe addition of 25 ml of 5% sodium hydroxide. The phases were separatedand the organic phase was further extracted with three 50 ml portions of5% sodium hydroxide and three 50 ml portions of water. The organicsolution was dried with anhydrous magnesium sulfate and the solventstripped using aspirator and high vacuum systems. The product was 5.0 gof a yellow liquid. The infrared spectrum (between salt plates) showedtwo carbonyl absorptions at 1718 cm⁻¹ (imide) and 1642 cm⁻¹ (amide). TheNMR spectrum showed the anticipated aromatic ring (7.5-8.0 ppm,multiplet, 3H), the amide methylene hydrogens (2.9-3.8 ppm, broaddoublet, 4H) and the HALS group [4.4-4.9 ppm, multiplet, 1H; 0.5-2.3ppm, several multiplets including two singlets (1.2 and 1.3 ppm)].

EXAMPLE 9 Preparation ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(2,2,6,6-tetramethyl-4-piperidinylaminocarbonyl)phthalimide

A. From the acid chloride of Example 2:

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed 2.1 g (0.013mol) of 2,2,6,6-tetramethyl-4-amino-piperidine and 50 ml of 2%dimethylformamide in methylene chloride. To this was added triethylamine(2.8 g, 0.028 mol). This mixture was stirred and cooled during theaddition of 5.0 g (0.013 mol) of acid chloride of Example 2, accompaniedby an exotherm to 40° C. The reaction was allowed to stir at roomtemperature for 1 hour. The mixture was transferred to a separatoryfunnel with 100 ml methylene chloride, 150 ml water and 50 ml of 5%sodium hydroxide. The phases were separated and the aqueous phaseextracted with an additional 50 ml of methylene chloride. The organicsolutions were combined and washed with three 100 ml portions of water.The organic solution was dried with anhydrous magnesium sulfate and thesolvent stripped using aspirator and high vacuum systems. The productwas 1.1 g of a white solids. This solid was recrystallized from tolueneto give 0.8 g of white crystals, melting at 260°-262° C. The infraredspectrum (chloroform) showed the carbonyl absorption at 1710 cm⁻¹(imide) and 1665 cm⁻¹ (amide). The NMR spectrum showed the anticipatedaromatic ring (7.7-7.9 ppm, doublet, 1H; 8.0-8.3, multiplet, 2H), theamide N--H (5.9-6.1 ppm, doublet, 1H) and the HALS groups [4.2-4.9 ppm,multiplet, 2H; 0.8-2.3 ppm, several multiplets including two singlets(1.2 and 1.3 ppm)].

B. From trimethyl 1,2,4-benzenetricarboxylate:

Into a 100 ml flask equipped with reflux condenser and oil bath werecombined 2,2,6,6-tetramethyl-4-aminopiperidine (2.7 g, 0.017 mol),trimethyl 1,2,4-benzenetricarboxylate (2.0 g, 0.008 mol), potassiumt-butoxide (0.04 g) and 50 ml of mesitylene. This mixture was refluxed28 hours, cooled and transferred to a separatory funnel with 100 mlmethylene chloride. The organic solution was washed with three 50 mlportions of water and dried with anhydrous magnesium sulfate. Thesolvent was stripped using aspirator and high vacuum systems. Theresidue was mixed with 50 ml pentane and set aside for crystallizationof the product. The crystallized product was isolated by filtration,yielding 0.6 g of white crystals. This product was recrystallized fromtoluene, producing 0.1 g of white crystals with a melting point andinfrared spectrum in agreement with that obtained for the product fromprocedure A in this example.

EXAMPLE 10 Preparation of styrene/allylalcohol/N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-allyloxycarbonylphthalimidecopolymer

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed 5.0 g (0.013mol) of acid chloride of Example 2 and 50 ml of 2% dimethylformamide inmethylene chloride. This mixture was stirred during the addition of 2.9g (about 0.013 hydroxy equivalents) of RJ®-101 (a styrene/allyl alcoholcopolymer from Monsanto having 7.7±3 wt % hydroxy content). 2.8 g (0.028mol) triethylamine were added. The reaction was refluxed for 1.5 hours.The mixture was transferred to a separatory funnel with 150 ml methylenechloride and 100 ml of 5% sodium hydroxide. The phases were separatedand the organic phase was further extracted with three 50 ml portions of5% sodium hydroxide and 50 ml water. The organic solution was dried withanhydrous magnesium sulfate and the solvent stripped using aspirator andhigh vacuum systems. The product was 4.3 g of light yellow crystals. Thesolid was redissolved in a minimum amount of methylene chloride andprecipitated by dropwise addition to 800 ml of hexane. The solid wasisolated by filtration yielding 3.9 g. The infrared spectrum (KBrpellet) showed the carbonyl absorption at 1715 cm⁻¹ (imide and ester).The Tg was determined to be 87.6° C. Molecular weight data obtained fromgel permeation chromatography indicated an Mn of 1400 and an Mw of 2100(based on polystyrene standard). The NMR spectrum demonstrated thepresence of the HALS moiety in the high molecular weight material (twosinglets at 1.2 and 1.3 ppm) and the presence of aromatic hydrogens fromthe pendant phenyl groups.

EXAMPLE 11 Preparation of4,4'-[2,5-dioxa-1,6-dioxohexane-1,6-diyl]bis[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide]

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed 6.5 g (0.017mol) of acid chloride of Example 2 and 50 ml of 2% dimethylformamide inmethylene chloride. This mixture was stirred during the addition of 0.43g (0.007 mol) of ethylene glycol. 7.3 g (0.072 mol) of triethylaminewere added, accompanied by an exotherm to 40° C. The reaction wasrefluxed for 4 hours. Acid chloride (1.0 g, 0.003 mol) was added and thereflux continued for an additional 2 hours. The mixture was cooled andtransferred to a separatory funnel with 50 ml methylene chloride andextracted with one 100 ml portion of 5% sodium hydroxide, two 50 mlportions of 5% sodium hydroxide and three 50 ml portions of water. Theorganic solution was dried with anhydrous magnesium sulfate and thesolvent stripped using aspirator and high vacuum systems. The solidresidue was recrystallized from 95% ethanol. The recrystallized solidwas dissolved in methylene chloride and dried again with anhydrousmagnesium sulfate. The solvent was stripped using aspirator and highvacuum systems yielding 2.6 g of yellow solid melting at 70° C. Theinfrared spectrum (KBr pellet) showed the carbonyl absorption at 1715cm⁻¹ (imide and ester). The NMR spectrum showed the anticipated aromaticring (7.7-7.9 ppm, doublet, 1H; 8.3-8.5, multiplet, 2H), the HALS N-C-Hand the methylenes merged (4.2-5.0 ppm, multiplet with prominent singletat 4.7 ppm) and the HALS groups [1.1-2.3 ppm, several multipletsincluding two singlets (1.2 and 1.3 ppm)].

This same product can be prepared from ethylene bis trimellitate (AC-32,a product of Anhydride and Chemical Incorporated), using the proceduredescribed in Example 29. The commercial bis anhydride is a mixture andthe product obtained is not as pure as that prepared above.

EXAMPLE 12 Preparation of4,4'-[1,3-phenylenedi(oxycarbonyl)]-bis[N-(2,2,6,6-tetramethyl-4-piperidinyl]phthalimide

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed 5.0 g (0.013mol) of acid chloride of Example 2 and 50 ml of 2% dimethylformamide inmethylene chloride. This mixture was stirred during the addition of 1.43g (0.013 mol) of resorcinol. 2.8 g (0.028 mol) of triethylamine wereadded, accompanied by a small exotherm, but the temperature was keptbetween 20 and 25° C. by using an ice bath. The reaction was stirred atroom temperature for 2 hours. The mixture was transferred to aseparatory funnel with 50 ml water, the phases were allowed to separateand the aqueous solution was washed with 50 ml of fresh methylenechloride. The combined organic solutions were washed with two 50 mlportions of 5% sodium hydroxide. The organic material was then driedwith anhydrous magnesium sulfate and the solvent stripped usingaspirator and high vacuum systems. The product was 1.8 g of a yellowsolid melting at 130°-135° C. The infrared spectrum (KBr pellet) showedtwo carbonyl absorptions at 1710 and 1745 cm⁻¹ (imide and ester). TheNMR spectrum showed the anticipated aromatic rings (7.8-8.0 ppm,doublet, 1H; 8.4-8.6, multiplet, 2H; 7.0-7.6 ppm, multiplet withprominent peak at 7.2 ppm), the HALS group [4.4-4.9 ppm, multiplet, 1H;1.1-2.3 ppm, several multiplets including two singlets (1.2 and 1.3ppm)]. The UV spectrum showed an absorbance maximum (THF) at 300 nm.

EXAMPLE 13 Preparation ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-4[octylphenoxypoly(ethoxy)carbonyl]phthalimide

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed 5.0 g (0.013mol) of acid chloride of Example 2, 50 ml of 2% dimethylformamide inmethylene chloride and TRITON X-100® (octylphenoxypoly(ethoxy)ethanol, aproduct of Rohm and Haas Co., 4.6 g). 1.5 g (0.015 mol) triethylaminewere added, accompanied by a small exotherm. The reaction cleared, thena solid formed as the mixture was heated to reflux. The reaction wasrefluxed for 4 hours, then cooled to room temperature and transferred toa separatory funnel with 50 ml methylene chloride and 50 ml of 5% sodiumhydroxide. The phases were allowed to separate and the aqueous solutionwas washed with three 100 ml portions of fresh methylene chloride. Theorganic material was then dried with anhydrous magnesium sulfate and thesolvent stripped using aspirator and high vacuum systems. The productwas 6.0 g of a viscous liquid. The infrared spectrum (between saltplates) showed two carbonyl absorptions at 1710 and 1685 cm⁻¹ (imide andester). The NMR spectrum showed the anticipated aromatic rings (7.8-8.0ppm, doublet; 8.3-8.6, multiplet; 6.7-7.4 ppm, multiplet). The ethylenegroups were a prominent singlet at 4.7 (with several smaller peaks atthe base) and the HALS and octyl groups were present (0.6-2.3 ppm,several multiplets including a singlet at 0.8 ppm). The integration ofthis spectrum indicated that the sample contained considerable unreactedstarting alcohol. A crude assay based on this integration indicated thetitle compound was present in about 50%.

EXAMPLE 14 Preparation ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(allyloxycarbonyl)phthalimide

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed 5.0 g (0.013mol) of acid chloride of Example 2, 50 ml of 2% dimethylformamide inmethylene chloride and allyl alcohol (0.7 g, 0.012 mol). Triethylamine(2.8 g, 0.028 mol) was added, accompanied by an exotherm from roomtemperature up to 35° C. The reaction was cooled to room temperature andstirred for 1.5 hours, then transferred to a separatory funnel with 50ml methylene chloride and 50 ml of 5% sodium hydroxide. The phases wereallowed to separate and the aqueous solution was washed with anadditional 50 ml of fresh methylene chloride. The combined organicsolutions were then dried with anhydrous magnesium sulfate and thesolvent stripped using aspirator and high vacuum systems. The productwas 3.8 g of a yellow solid melting at 90°-93° C. The solid wasrecrystallized in methyl t-butyl ether, producing almost white crystalsmelting at 96°-98° C. The infrared spectrum (KBr pellet) showed thecarbonyl absorption at 1715 cm⁻¹ (imide and ester). The NMR spectrumshowed the anticipated aromatic ring (7.7-7.9 ppm, doublet, 1H; 8.2-8.5,multiplet, 2H), a typical allyl group pattern merging with the N--C--Hof the HALS group (4.8-6.3 ppm for allyl and 4.4-4.9 ppm for HALS,several multiplets, 6H) and the rest of the HALS group [ 0.8-2.3 ppm,several multiplets including two singlets (1.2 and 1.3 ppm)].

EXAMPLE 15 Reaction of JEFFAMINE® D-230 with the Acid Chloride ofExample 2

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed 5.0 g (0.013mol) of acid chloride of Example 2, 50 ml of 2% dimethylformamide inmethylene chloride and JEFFAMINE® D-230 (an amine terminatedpolypropylene oxide, product of Texaco Chemical Co., 1.5 g). The amineaddition caused a small exotherm. Triethylamine (2.8 g, 0.028 mol) wasadded, accompanied by an exotherm from room temperature up to 35° C. Thereaction was stirred at ambient temperature for 2.5 hours. The mixturewas transferred to a separatory funnel with 100 ml methylene chlorideand 100 ml of 5% sodium hydroxide. The phases were allowed to separateand the organic was washed with two 50 ml portions of 5% sodiumhydroxide and three 50 ml portions of water. The organic solution wasthen dried with anhydrous magnesium sulfate and the solvent strippedusing aspirator and high vacuum systems. The product was 4.8 g of whitecrystals. The infrared spectrum (KBr pellet) showed two carbonylabsorptions at 1710 and 1650 cm⁻¹ (imide and amide). The Tg wasdetermined to be 61.6° C. The NMR spectrum showed the anticipatedaromatic ring (7.7-7.9 ppm, doublet; 8.0-8.3, multiplet); and thepresence of the HALS group, indicated by two singlets at 1.2 and 1.3ppm.

EXAMPLE 16 Reaction of the Acid Chloride of Example 2 withPoly(butadiene) diol

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed 1.9 g (0.005mol) of acid chloride of Example 2, 50 ml of 2% dimethylformamide inmethylene chloride and polybutadiene diol (nominal M. W. 2800, a productof Scientific Polymer Products, Inc.) (5.0 g). Triethylamine (1.0 g,0.01 mol) was added, accompanied by a small exotherm. The reaction wasstirred at room temperature for 2 hours. The mixture was transferred toa separatory funnel with 100 ml methylene chloride and washed with three50 ml portions of 5% sodium hydroxide (making the best possibleseparations of the emulsified mixture). The aqueous washes were combinedand further diluted with 100 ml water and extracted with 250 mlmethylene chloride. The organic solutions were combined then dried withanhydrous magnesium sulfate and the solvent stripped using aspirator andhigh vacuum systems. The product was 5.4 g of viscous dark yellowliquid. The infrared spectrum (between salt plates) showed severalcarbonyl absorptions with a broad major absorption at 1710 cm⁻¹. The NMRspectrum demonstrated the presence of the aromatic rings and intensemethylene absorbances from the polybutadiene. The presence of the HALSgroup was indicated by two singlets at 1.2 and 1.3 ppm.

EXAMPLE 17 Preparation ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-4-[(4-morpholinyl)carbonyl]phthalimide

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed 5.0 g (0.013mol) of acid chloride of Example 2 and 50 ml of 2% dimethylformamide inmethylene chloride. Morpholine (4.0 g, 0.046 mol) was added, accompaniedby a strong exotherm, and an ice water bath was used to maintain thereaction temperature below 30° C. After complete addition of themorpholine, the reaction was stirred at room temperature for 1 hour thentransferred to a separatory funnel with 100 ml methylene chloride andwashed with three 50 ml portions of 5% sodium hydroxide and three 50 mlportions of water. The organic solution was dried with anhydrousmagnesium sulfate and the solvent stripped using aspirator and highvacuum systems. The product was 4.4 g of white solids. This material wasrecrystallized from hexanes providing 2.3 g of white crystals melting at179°-184° C. The infrared spectrum (KBr pellet) showed two carbonylabsorptions at 1710 and 1640 cm⁻¹ (imide and amide). The NMR spectrumshowed the anticipated aromatic ring (7.5-8.0 ppm, multiplet, 3H), themorpholine ring (3.3-4.0 ppm, broad singlet, 8H) and the HALS group[4.4-4.9 ppm, multiplet, 1H; 0.9-2.3 ppm, several multiplets includingtwo singlets (1.2 and 1.3 ppm)] .

EXAMPLE 18 Preparation ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-4-{[4-(2,2-di[methoxycarbonyl]ethenyl)phenoxy]carbonyl}phthalimide

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed 1.9 g (0.005mol) of acid chloride of Example 2, 50 ml of 2% dimethylformamide inmethylene chloride, dimethyl (p-hydroxybenzylidene)malonate (2.6 g,0.011 mol) and triethylamine (1.0 g, 0.01 mol). The reaction wasrefluxed for 3 hours then cooled and transferred to a separatory funnelwith 100 ml methylene chloride and washed with three 50 ml portions of5% sodium hydroxide and three 50 ml portions of water. The organicsolutions were combined, then dried with anhydrous magnesium sulfate andthe solvent stripped using aspirator and high vacuum systems. Theproduct was 5.7 g of slightly yellow solid. This material was heatedwith a solvent mixture of 20% 2-propanol and 80% hexanes, then cooledand the insoluble material isolated by filtration (2.8 g yellow solidwas collected, melting about 135° C.). This was slurried with hottetrahydrofuran and filtered hot. The tetrahydrofuran was stripped togive 2.4 g of slightly yellow solid melting at 55°-58° C. The infraredspectrum (chloroform) showed a broad carbonyl absorption at 1710 cm⁻¹(imide and ester). The UV spectrum showed an absorbance maximum at 292nm with molar absorptivity 20000.

EXAMPLE 19 Preparation ofN-(2,2,6,6-tetramethyl-4-piperidiny1)-4-{[2-hydroxy-3-(alkyl-[C₁₂₋₁₄]oxy)propoxy]carbonyl}phthalimide

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed the HALS-acidof Example 1 (7.0 g (0.021 mol), EPOXIDE® 8 (a mixture of1,2-epoxy-3-(alkyl[C₁₂₋₁₄ ]oxy)propane, product of Procter and Gamble)(4.3 g), ADOGEN 464® (methyltrialkyl[C₈₋₁₀ ]ammonium chloride, fromAshland Chemical Co.) (0.11 g) and 80 ml of dimethylformamide. Thereaction was refluxed for 4 hours and 20 minutes then cooled. Themixture was transferred to a separatory funnel with 200 ml methylenechloride and washed with three 100 ml portions of 5% sodium hydroxideand two 100 ml portions of water. The organic solution was dried withanhydrous magnesium sulfate and the solvent stripped using aspirator andhigh vacuum systems. The stripped residue still contained residualdimethylformamide and was therefore dissolved in methyl t-butyl etherand washed with three 100 ml portions of water. The organic solution wasdried and stripped as before and the residue recrystallized fromhexanes, then a second time from 25% aq. ethanol. The recrystallizedproduct was dissolved in methylene chloride and dried and stripped asdescribed previously. The product was next dissolved in 10 ml methylenechloride and precipitated into 600 ml pentane. The product was isolatedby filtration as 2.7 g of white crystals melting at 89°-92° C. Theinfrared spectrum showed a broad carbonyl absorption at 1710 cm⁻¹ (imideand ester) and a broad hydroxyl and amine absorption at 3300-3700 cm⁻¹.

EXAMPLE 20 Preparation ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(n-butoxycarbonyl)phthalimide

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed the HALS-acidof Example 1 (3.3 g (0.01 mol), n-butylbromide (3.13 g, 0.022 mol),Adogen 464™ (Ashland Chemical Co.) (0.19 g), sodium carbonate (6.64 g,0.044 mol) and 50 ml of dimethylformamide. The reaction was heated to80°-90° C. for 2 hours, allowed to stand at ambient temperature for 15hours then heated again at 80°-90° C. for 6.5 additional hours. Themixture was transferred to a separatory funnel with 100 ml methylt-butyl ether and 500 ml water. The phases were agitated then allowed toseparate. The ether solution was retained and the aqueous solution wasextracted with 100 ml fresh ether. The combined ether extracts weredried with anhydrous magnesium sulfate and stripped using aspirator andhigh vacuum systems. A white solid residue was isolated using a smallamount of pentane (the product is quite soluble in this solvent). Theproduct was 3.0 g of white crystals melting at 90°-92° C. The infraredspectrum (chloroform) showed a broad carbonyl absorption at 1700 cm⁻¹(imide and ester). The NMR spectrum showed the anticipated aromatic ring(7.7-8.5 ppm, multiplet, 3H), the --N--C--H and --O--CH₂ merged(4.2-4.8, triplet and multiplet, 3H) and the rest of the HALS group andbutyl group [0.9-2.3 ppm, several multiplets including two singlets (1.2and 1.3 ppm)].

EXAMPLE 21 Preparation ofN-(2,2,6,6-tetramethyl-4-piperidiny-1)-4-(n-octadecyloxycarbonyl)phthalimide

Into a suitable flask were placed 7.0 g of octadecanol, 5.7 gtriethylamine, 0.1 g of 4-(dimethylamino)pyridine and about 100 ml ofdry methylene chloride. The mixture was stirred during the addition of10.0 g of the acid chloride of Example 2 over a 10 minute period. Thereaction was continued at room temperature for 2 hours. The resultingsuspension was suction filtered to remove precipitated salt which waswashed with fresh methylene chloride. The combined methylene chlorideliltrates were placed in a separatory funnel and washed with dilute aq.hydrochloric acid, water and finally with 5% sodium hydroxide. Thesolution was dried using anhydrous magnesium sulfate and the solventstripped to yield 14.6 g (97% of theoretical) of a yellow wax. Theinfrared spectrum of this material showed two carbonyl absorptions(imide and ester) at 1715 and 1725 cm⁻¹. The material was examined usingliquid chromatography which indicated approximately 4.5% residualoctadecanol contaminated the product.

EXAMPLE 22 Reaction of JEFFAMINE® M-300 with the Acid Chloride ofExample 2

Into a suitable flask were placed 4.5 g of JEFFAMINE® M-300 (an etherand amine terminated polypropylene oxide, a product of Texaco ChemicalCompany), 3.4 g triethylamine, 0.1 g of 4-(dimethylamino)pyridine andabout 100 ml of dry methylene chloride. The mixture was stirred duringthe addition of 5.0 g of the acid chloride of Example 2 over a 10 minuteperiod. The reaction was allowed to continue at room temperature for 2hours. The resulting suspension was suction filtered to removeprecipitated salt which was washed with fresh methylene chloride. Thecombined methylene chloride flitrates were placed in a separatory funneland washed with dilute aqueous hydrochloric acid, water and finally with5% sodium hydroxide. The solution was dried using anhydrous magnesiumsulfate and the solvent stripped to yield 8.3 g (99% of theoretical) ofa yellow oil. The infrared spectrum of this material showed two carbonylabsorptions (imide and amide) at 1711 cm⁻¹ and 1645 cm⁻¹ (broad). Thematerial was examined using liquid chromatography which showed that thehigh molecular weight material had acquired a UV absorption, anindication that the reaction had proceeded as expected.

EXAMPLE 23 Reaction of the Acid Chloride of Example 2 with DURACARB® 120

Into a suitable flask were placed 6.1 g of DuraCarb® 120 (ahydroxy-terminated aliphatic polycarbonate product of PPG Industries,having 4.2 wt % hydroxyl groups), 3.4 g triethylamine, 0.1 g of4-(dimethylamino)pyridine and about 100 ml of dry methylene chloride.The mixture was stirred during the addition of 5.0 g of the acidchloride of Example 2 over a 10 minute period. The reaction was allowedto continue at room temperature for 2 hours. The resulting suspensionwas suction filtered to remove precipitated salt, which was washed withfresh methylene chloride. The combined methylene chloride filtrates wereplaced in a separatory funnel and washed with dilute aqueoushydrochloric acid, water and finally, with 5% sodium hydroxide. Thesolution was dried using anhydrous magnesium sulfate and the solventstripped to yield 9.5 g (95% of theoretical) of a viscous yellow oil.The infrared spectrum of this material showed two carbonyl absorptions(imide and ester) at 1715 and 1740 cm⁻¹. The material was examined usingliquid chromatography which showed that the high molecular weightmaterial had acquired an enhanced UV absorption, an indication that thereaction had proceeded as expected.

EXAMPLE 24 Reaction of the Acid Chloride of Example 2 with TONE® 220

Into a suitable flask were placed 7.5 g of Tone® 220 (ahydroxy-terminated aliphatic polycaprolactone product of Union CarbideCompany, having an assay of 3.4 wt % hydroxyl groups), 3.2 gtriethylamine, 0.1 g of 4-(dimethylamino)pyridine and about 100 ml ofdry methylene chloride. The mixture was stirred during the addition of5.0 g of the acid chloride of Example 2 over a 10 minute period. Thereaction was allowed to continue at room temperature for 2 hours. Theresulting suspension was suction filtered to remove precipitated salt,which was washed with fresh methylene chloride. The combined methylenechloride filtrates were placed in a separatory funnel and washed twicewith dilute aqueous hydrochloric acid. During the second wash anemulsion formed that was broken with the addition of sodium chloride.The aqueous acidic washes were back-extracted with fresh methylenechloride. The combined organic solutions were then washed with potassiumbicarbonate solution. The solution was dried using anhydrous magnesiumsulfate and the solvent stripped to yield 7.1 g (62% of theoretical) ofa yellow oil. The infrared spectrum of this material showed a broadcarbonyl absorption (imide and ester) at 1700-1750 cm⁻¹. The materialwas examined using liquid chromatography which showed that the highmolecular weight material had acquired an enhanced UV absorption, anindication that the reaction had proceeded as expected.

EXAMPLE 25 Reaction of the Acid Chloride of Example 2 with Poly(ethyleneglycol), methyl ether

Into a suitable flask were placed 5.0 g of poly(ethylene glycol), methylether (approximate molecular weight of 350), 3.6 g triethylamine, 5.5 gof the acid chloride of Example 2 and 75 ml of acetone. The reaction wasstirred and warmed to a reflux which was continued for a short period.The reaction was allowed to stand at room temperature over night. Theresulting suspension was suction filtered to remove precipitated saltand stripped. The residual oil was dissolved in methylene chloride andwashed twice with water. The solution was dried using anhydrousmagnesium sulfate and the solvent stripped to yield 7.7 g (82% oftheoretical) of a viscous yellow oil. The infrared spectrum of thismaterial showed a carbonyl absorption (imide and ester) at 1715 cm⁻¹ anda broad C--O absorption at 1100-1110 cm⁻¹. The material was examinedusing liquid chromatography which showed that the high molecular weightmaterial had acquired an enhanced UV absorption, an indication that thereaction had proceeded as expected.

EXAMPLE 26 Preparation ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-4-[(2-hydroxy-2-phenylethoxy)carbonyl]phthalimide

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed the HALS ofExample 1 (5.0 g, 0.015 mol), styrene oxide (1.6 g, 0.013 mol), ADOGEN®(Ashland Chemical Co.) (0.15 g) and 60 ml of dimethylformamide. Thereaction was refluxed for 5 hours then cooled. The mixture wastransferred to a separatory funnel with 100 ml methylene chloride andwashed with 200 ml of 2.5% sodium hydroxide. Additional methylenechloride, 100 ml, was added and the solution extracted with two 100 mlportions of 5% sodium hydroxide and then 100 ml water. The organicsolution was then dried with anhydrous magnesium sulfate and the solventstripped using aspirator and high vacuum systems. The solid residue (2.9g) was recrystallized from aqueous ethanol, then recrystallized againfrom methyl t-butyl ether/hexanes. After high vacuum removal of residualsolvent, the product weighed 0.6 g and melted at 144°-146° C. Theinfrared spectrum (in chloroform) showed a broad carbonyl absorption at1710 cm⁻¹ (imide and ester). The structure of this material was furtherconfirmed using proton NMR spectroscopy.

EXAMPLE 27 Preparation of4,4'-[4,13-dihydroxy-1,16-dioxo-2,6,11,15-tetraoxa-hexadecane-1,16-diyl]bis[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide]

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed the HALS ofExample 1 (4.3 g, 0.013 mol), 1,4-butane diol diglycidyl ether (1.3 g,0.006 mol), ADOGEN® 464 (Ashland Chemical Co.) (0.13 g) and 50 ml ofdimethylformamide. The reaction was refluxed for 5 hours, then filtered.The filtered mixture was poured into 200 ml water, producing aprecipitate. The solution was stirred for 5 minutes then the solid wascollected by filtration, slurried with another 500 ml water, stirred 30minutes, then isolated again. The wet solid was dissolved intetrahydrofuran and dried with anhydrous magnesium sulfate. The solventwas stripped and the resulting light tan crystals (4.0 g) wererecrystallized from about 75 ml of 95% ethanol. The recrystallized solidwas dissolved in tetrahydrofuran, dried and stripped as before withadditional removal of solvent under high vacuum. The result was 2.4 g ofwhite crystals melting at 117°-122° C. The infrared spectrum (inchloroform) showed a broad carbonyl absorption at 1710 cm⁻¹ (imide andester) and a broad OH and NH absorption at 3100-3600 cm⁻¹.

EXAMPLE 28 Preparation ofN-(1-acety1-2,2,6,6-tetramethyl-4-piperidinyl)-4-(ethoxycarbonyl)phthalimide

Into a 125 ml reaction flask equipped with a magnetic stirrer,thermometer, condenser and nitrogen atmosphere were placed the HALS ofExample 4 (0.9 g, 0.0025 mol), 4-dimethylaminopyridine (0.03 g) and 25ml of acetic anhydride. The reaction was refluxed for 2 hours, thenpoured into a beaker containing 200 ml ice water. A brown oil separatedimmediately and the mixture was stirred until the oil solidified into atan solid. This solid was isolated by filtration and washed on thefilter funnel with several portions of water. The wet solid wasdissolved in 50 ml methylene chloride and dried with anhydrous magnesiumsulfate. The solvent was stripped to give 0.9 g of light tan crystalsmelting at 119°-121° C. The infrared spectrum (in chloroform) showed abroad carbonyl absorption at 1710 cm⁻¹ (imide and ester) and an amidecarbonyl at 1615 cm⁻¹.

EXAMPLE 29 Preparation of4,4,-(4-acetoxy-2,6-dioxa-1,7-dioxoheptane-1,7-diyl)bis[N-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)phthalimide]

A. Reaction of glycerol acetate his trimellitate with2,2,6,6-tetramethyl-4-aminopiperidine

Into a 1 liter flask equipped with mechanical stirrer and nitrogenatmosphere were combined glycerol acetate his trimellitate (33.8 g, 0.07mol, this ester is available commercially as AC-32, a product ofAnhydrides and Chemicals Incorporated) and dimethylformamide (200 ml).This mixture was warmed to 50° C. to dissolve the anhydride and2,2,6,6-tetramethyl-4-aminopiperidine (25.0 g, 0.16 mol) was added whichformed an immediate precipitate. The reaction was stirred for 2 hourswhile cooling to ambient temperature. Methyl t-butyl ether (400 ml) wasadded to the mixture and the solid product isolated by filtration. Thefiltered solid was slurried three times with 300 ml portions of etherand filtered each time. The isolated solid was placed under high vacuumand heated to about 170° C. for 1 hour. The resulting white powderweighed 54.6 g and melted at 203°-207° C. By infrared spectroscopy, thismaterial was identified as the bis amic acid (internal salt) with estercarbonyl banding at 1715 cm⁻¹ amide and acid salt carbonyl banding1540-1620 cm⁻¹. Upon heating to 270° C., this amic acid further reactedto form the bis imide. The infrared spectrum had a broad intensecarbonyl band at about 1710 cm⁻¹ and only small residual banding in theregion 1500-1680 cm⁻¹.

B. Preparation of the title compound

Into a 250 ml flask equipped with reflux condenser were placed the amicacid prepared in step A of this example (10.0 g, 0.013 mol) and 100 mlacetic anhydride. The mixture was refluxed 2 hours, during which timethe amic acid slowly went into solution. The reaction mixture was pouredinto a beaker packed with ice and brought to pH 14 using 45% potassiumhydroxide (aqueous). A brown gum separated from solution and wasisolated by decanting away the aqueous solution. The gum was dissolvedin methylene chloride and transferred to a separatory funnel where itwas washed with 10% aqueous sodium hydroxide, 5% aqueous hydrochloricacid and saturated aqueous sodium bicarbonate. The organic phase wasdried with anhydrous magnesium sulfate and the solvent was strippedusing aspirator and high vacuum systems, yielding 5.6 g of light tansolid. The infrared spectrum of this material showed an intense carbonylabsorption at 1710 cm⁻¹ (ester and imide) and another carbonylabsorption at 1620 cm⁻¹ (amide).

EXAMPLE 30 Accelerated Weathering of ABS containingN-(2,2,6,6-tetramethy1-4-piperidiny1)-4-(2,2,6,6-tetra-methyl-4-piperidinyloxycarbonyl)phthalimide

A. Sample Preparation

ABS polymer (Dow 500 natural, dried for hours at 90° C.) was used toprepare test specimens for weathering. The ABS compositions preparedwere:

1. 0.42 phr HALS of Example 5 and 0.25 phr Tinuvin P

2. 0.25 phr Tinuvin P

3. 0.50 phr Tinuvin P

4. none (control)

The additives were first mixed with the polymer and then the blend wasextruded twice in a Brabender Prep Center Extruder at 230° C. Thecontrol was extruded twice, even though no stabilizer was added. Theresulting stabilized polymer was pelletized and molded into plaques on aNewbury 25 ton injection molder at 400° F.

B. Weathering Test

The plaques prepared above were weathered in an Atlas Ci65Weather-0-Meter using a 6500 watt xenon arc source (inner and outerborosilicate filters, irradiance 0.38 w/m2 at 340 nm) and a cycle timeof 3 hours (2 hours of light at 70° C. black panel temperature with 50%relative humidity and a 20 minute front spray during the first hour, and1 hour dark period at 38° C. with 100% relative humidity and continualback spray). The samples were removed from the test instrument and colordevelopment was measured by on a Gardner colorimeter. Increase inyellowness index (YID) was monitored and the values obtained from anaverage of three samples. The results are shown in TABLE I. Theseresults demonstrate that the use of a hindered amine of this inventionin conjunction with a known UV absorber enhances the stability of ABS toaccelerated weathering. The effect of the hindered amine (0.42 phr) isdistinct from that ofthe UV absorber (0.25 phr) as demonstrated bycontrols which show that the UV absorber alone (0.25 phr) and at twicethe level (0.50 phr) do not provide the enhanced degree of stabilizationobserved when the hindered amine is present.

                  TABLE I                                                         ______________________________________                                        Accelerated Weathering of ABS Containing HALS                                             YID after exposure                                                Stabilized Polymer                                                                        (days)                                                            Composition 2      7      14   21   28   35   48                              ______________________________________                                        1           18.9   14.2   14.3 14.4 16.1 18.0 21.9                            2           18.7   13.6   14.1 14.8 17.2 19.6 24.9                            3           19.2   14.6   16.3 17.6 20.7 23.6 29.7                            4           24.0   26.8   31.8 35.1 39.0 42.8 47.9                            ______________________________________                                    

The present invention may be embodied in other specific forms withoutdeparting from the spirit or essential attributes thereof and,accordingly, reference should be made to the appended claims, ratherthan to the foregoing specification as indicating the scope of theinvention.

I claim:
 1. A polymeric composition stabilized against degradativeeffects of heat or light comprising a synthetic or natural polymer mixedwith a compound of formula I in an amount effective to stabilize thepolymer against the degradative effects of heat or light, wherein thecompound of formula I is: ##STR29## wherein R¹ is hydrogen orsubstituted or unsubstituted alkyl of 1-4 carbons; ##STR30## R² is oxyl,hydroxy, substituted or unsubstituted aliphatic acyl of 1-20 carbons,substituted or unsubstituted alicyclic acyl of 6-14 carbons, substitutedor unsubstituted aryl acyl of 7-11 carbons, substituted or unsubstitutedaraliphatic acyl of 7 22 carbons, --C(═O) N(R⁴)(R⁵) or C(═O)--O--R⁶ ;R³is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted araliphatic of 7-22 carbons, alkoxyalkyl of2-21 carbons or --CH₂ --C(═O)--O--R⁷ ; R⁴, R⁵ and R⁷ are independentlyhydrogen substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted aryl of 6-10 carbons, substituted orunsubstituted araliphatic of 7-22 carbons or a substituted orunsubstituted alicyclic group of 5-12 carbons which may optionallycontain --N(R⁹)-- as a group member and R⁴ and R⁵ may optionally belinked together to form an alicyclic group of 5-7 atoms or may be linkedtogether through a heteroatom --N(R¹⁰)-- or --O-- to form a heterocyclicring of 5-7 atoms; R⁶ is substituted or unsubstituted aliphatic of 1-20carbons, substituted or unsubstituted aryl of 6-10 carbons, substitutedor unsubstituted araliphatic of 7-22 carbons or a substituted orunsubstituted alicyclic group of 5-12 carbons which may optionallycontain --N(R⁹)-- as a group member; R⁸ is hydroxy, --O.sup.⊖, halogen--NH₂, --NHNH₂ or the residue from a substituted or unsubstituted,compound or polymer containing at least one hydroxy, amine, mercaptan orhydrazine group or molecular mixture thereof, whereinhydroxy-containing, amine-containing, mercaptan-containing orhydrazine-containing polymers may be backbone, pendant or terminallyfunctionalized; R⁹ and R¹⁰ are independently hydrogen or substituted orunsubstituted alkyl of 1-4 carbons; s is an integer of 1 to a numbercorresponding to the number of free valences of R⁸ ; A is an anionchloride, bromide, sulfate, acid sulfate, sulfite, acid sulfite,p-toluenesulfonate, phenylsulfonate, methylsulfonate, phosphate, acidphosphate, carboxylate from any carboxylic acid or R⁸ when R⁸ is--O.sup.⊖ ; substitutents for the alkyl, aliphatic, aryl, araliphatic,alicyclic, aliphatic acyl, aryl acyl or araliphatic acyl radicals, R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ independently are one or more ofaliphatic of 1-8 carbons, alkoxy of 1-4 carbons, alkanoyl of 1-12carbons, alkanoyloxy of 1-12 carbons, alkoxycarbonyl of 2-5 carbons,arylcarbonyl of 7-11 carbons, acryloyloxy, methacryloyloxy, aryloxy of6-10 carbons, aralkyl of 7-10 carbons, aryloxycarbonyl of 7-11 carbons,aryl of 6-10 carbons, amino, hydroxy, carboxy, nitrile, chloro, bromo,epoxy, vinyl, alkyl mercapto of 1-4 carbons, benzoyloxy, aryl mercaptoof 6-10 carbons, alkylamino of 1-4 carbons, dialkylamino of 2-8 carbons,arylamino of 6-10 carbons, aryl alkyl amino of 7-10 carbons ortrialkoxysilyl of 3-9 carbons.
 2. The stabilized polymeric compositionof claim 1 wherein for the compoundR is hydrogen or methyl; R² issubstituted or unsubstituted alkanoyl of 2-5 carbons, aliphatic acyl of2-5 carbons, substituted or unsubstituted aryl acyl of 7-11 carbons orsubstituted or unsubstituted araliphatic acyl of 7-22 carbons; R³ ishydrogen, substituted or unsubstituted alkyl of 1-4 carbons, substitutedor unsubstituted alkoxyalkyl of 2-6 carbons, substituted orunsubstituted araliphatic of 7-10 carbons, allyl or CH₂ --C(═O)--O--R⁷ ;R⁴, R⁵ and R⁷ are independently hydrogen substituted or unsubstitutedalkyl of 1-4 carbons, substituted or unsubstituted cyclohexyl,substituted or unsubstituted benzyl or substituted or unsubstitutedphenyl; and R⁶ is substituted or unsubstltuted alkyl of 1-6 carbons,substituted or unsubstituted aralkyl of 7 to 10 carbons or substitutedor unsubstituted phenyl.
 3. The stabilized polymeric composition ofclaim 1 wherein for the compoundR is hydrogen; R² is acetyl, substitutedor unsubstituted benzoyl or --C(═O)--O--R⁶ ; R³ is hydrogen, substitutedor unsubstituted alkyl of 1-4 carbons, allyl, benzyl or --CH₂--C(═O)--O--R⁷.
 4. The stabilized polymeric composition of claim 3wherein for the compound R³ is hydrogen and A is chloride.
 5. Thestabilized polymeric composition of claim 3 wherein for the compound R³is hydrogen and A is R⁸ when R⁸ is --O.sup.⊖.
 6. The stabilizedpolymeric composition of claim 1 wherein for the compound, when s is1:R⁸ is 1-morpholinyl, 1-piperidinyl, 1-pyrrolidinyl or R¹¹ --Y--; Y is--O--, --N(R¹²)--, --S--, --C(═O)--NH--NH--, --NH--NH--,--NH--C(═O)--NH--NH--, --O--C(═O)--NH--N--H--,--NH--C(═O)--C(═O)--NH--NH-- or --O--C(═O)--C(═O)--NH--NH--; R¹¹ ishydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted aryl of 6-10 carbons, substituted orunsubstituted araliphatic of 7-22 carbons, a substituted orunsubstituted alicyclic group of 5-12 carbons which may optionallycontain --N(R¹³)-- as a group member, trialkylsilylalkyl of 5-20carbons, alkyldiarylsilylalkyl of 15-20 carbons, alkoxyalkyl of 3-20carbons, substituted or unsubstituted3-(2H-benzotriazol-2-yl)-2-hydroxybenzyl, substituted or unsubstituted4-benzoyl-3-hydroxyphenoxymethyl, substituted or unsubstituted4-benzoyl-3-hydroxyphenoxyethyl, trialkoxysilylpropyt of 4-15 carbons,substituted or unsubstituted 4-[2,2,-di(methoxycarbonyl)ethenyl]phenylor polyalkyl having a formula CH₃ --(CH₂)_(c) -- in which c is aninteger of 25-50; R¹² is hydrogen, substituted or unsubstitutedaliphatic of 1-20 carbons, substituted or unsubstituted aryl of 6-10carbons, substituted or unsubstituted araliphatic of 7-22 carbons or asubstituted or unsubstituted alicyclic group of 5-12 carbons which mayoptionally contain --N(R¹⁴)-- as a group member; and R¹³ and R¹⁴ areindependently hydroxy, substituted or unsubstituted aliphatic acyl of1-20 carbons, substituted or unsubstituted alicyclic acyl of 6-14carbons, substituted or unsubstituted aryl acyl of 7-11 carbons,substituted or unsubstituted araliphatic acyl of 7-22 carbons,--C(═O)--N(R⁴)(R⁵), --C(═O)--O--R⁶ substituted or unsubstitutedaliphatic of 1-20 carbons, substituted or unsubstituted araliphaticradical of 7-22 carbons, alkoxyalkyl of 2-21 carbons or --CH₂--C(═O)--O--R; where the substituents for R¹¹, R¹², R¹³ and R¹⁴independently are one or more of aliphatic of 1-8 carbons, alkoxy of 1-4carbons, alkanoyl of 1-12 carbons, alkanoyloxy of 1-12 carbons,alkoxycarbonyl of 2-5 carbons, arylcarbonyl of 7-11 carbons,acryloyloxy, methacryloyloxy, aryloxy of 6-10 carbons, aralkyi of 7-10carbons, aryloxycarbonyl of 7-11 carbons, aryl of 6-10 carbons, amino,hydroxy, carboxy, nitrile, chloro, bromo, epoxy, vinyl, alkyl mercaptoof 1-4 carbons, benzoyloxy, aryl mercapno of 6-10 carbons, alkylamino of1-4 carbons, dialkylamino of 2-8 carbons, arylamino of 6-10 carbons,aryl alkyl amino of 7-10 carbons or trialkoxysilyl of 3-9 carbons. 7.The stabilized polymeric composition of claim 1 wherein for the compoundwhen s is at least 1, R⁸ is one of the following divalent, trivalent andpolyvalent groups (i)-(xi) with the understanding that any valence notsatisfied by attachment to the acyl group of formula I is satisfied by agroup R¹⁵.R¹⁵ is hydrogen, substituted or unsubstituted aliphatic of1-20 carbons, substituted or unsubstituted aryl of 6-10 carbons,substituted or unsubstituted araliphatic of 7-22 carbons and substitutedor unsubstituted alicyclic of 5-12 carbons, substituted or unsubstitutedaliphatic acyl of 1-20 carbons, substituted or unsubstituted alicyclicacyl of 6-14 carbons, substituted or unsubstituted aryl acyl of 7-11carbons or substituted or unsubstituted araliphatic acyl of 7-22carbons;(i) 1,4-piperazindiyl; (ii) --Y--R¹⁶ --Y-- wherein Y is --O--,--N(R¹²)--, --S--, --C(═O)--NH--NH--, --NH--NH--, --NH--C(═O)--NH--NH--, --O--C(═O)--NH--NH--, --NH--C (═0) --C(═O) --NH--NH-- or--O--C(═O)--C(═O)--NH--NH--; R¹⁶ is a substituted or unsubstitutedaliphatic diradical of 2-20 carbons, substituted or unsubstitutedalicyclic diradical of 5-20 carbons, substituted or unsubstituted aryldiradical of 6-10 carbons, substituted or unsubstituted araliphaticdiradical of 7-22 carbons, where the aliphatic, alicyclic andaraliphatic diradicals may contain heteroatoms nitrogen, sulfur oroxygen, 4,4'-oxybis-(phenylene)-diyl, 1,2-phenylenebis(oxyalkyl) of10-14 carbons, 1,4-phenylenebis(oxyalkyl) of 10-14 carbons,oxybis(dimethylsilylpropyl), 4,4'-biphenyldiyl,2,2-propane-bis(phenylene)-p,p'-diyl, diphenylsulfone-4,4'-diyl; apoly(alkoxy) dialkyl diradical having a formula ##STR31## in which R¹⁷is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons orsubstituted or unsubstituted araliphatic of 7-10 carbons and d is aninteger of 1 or 2 and e is an integer of 0-350; a polycarbonatediradical having a formula ##STR32## in which f and g are independentlyintegers of 1-5 and R¹⁸ and R¹⁹ are independently a substituted orunsubstituted aliphatic diradical of 2-20 carbons, substituted orunsubstituted alicyclic diradical of 5-12 carbons, substituted orunsubstituted aryl diradical of 6-10 carbons or substituted orunsubstituted araliphatic diradical of 7-22 carbons; a diester orpolyester diradical having a formula ##STR33## in which h is an integerof 0 to 10; an unsaturated terminally functional polyolefin diradicalhaving a molecular weight of from about 2000 to about 3500; apoly(mercaptoether) diradical having a formula ##STR34## in which i isan integer of 2-12; an unsaturated copolymer diradical having a formula##STR35## in which m is an integer of 5-10 and j and k are componentfractions, k is about 0.1 to about 0.3 and j is 1-k; apoly(organosiloxane) diradical having a formula ##STR36## in which n isan integer of 5-3000 and q is an integer of 3 or 4; or a polyesterdiradical having a formula ##STR37## in which b is an integer of 0-10and may be different for each of the two repeating groups, and R²⁰ is analiphatic diradical of 2 to 4 carbons;(iii)4-aza-1,7-dioxaheptane-1,4,7-triyl; ##STR38## wherein R²¹ is asubstituted or unsubstituted aliphatic triradical of 3-20 carbons,substituted or unsubstituted aryl triradical of 6-13 carbons orsubstituted or unsubstituted araliphatic triradical of 7-22 carbons,where the aliphatic, alicyclic and araliphatic triradicals may containheteroatoms nitrogen, sulfur or oxygen, with the proviso that theheteroatoms are separated from each other and Y by at least one carbonatom, or a polyester triradical having a formula ##STR39## in which b isan integer of 0-10 and may be different for each of the three repeatinggroups where R²² is an aliphatic triradical of 3 to 8 carbons; ##STR40##wherein R²³ is a substituted or unsubstituted aliphatic tetraradical of4-20 carbons, substituted or unsubstituted alicyclic tetraradical of6-16 carbons, substituted or unsubstituted aryl tetraradical of 6-14carbons or substituted or unsubstituted araliphatic tetraradical of 7-22carbons; ##STR41## wherein ##STR42## ##STR43## where the substituentsfor R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²¹ and R²³ independently are one or moreof aliphatic of 1-8 carbons, alkoxy of 1-4 carbons, alkanoyl of 1-12carbons, alkanoyloxy of 1-12 carbons, alkoxycarbonyl of 2-5 carbons,arylcarbonyl of 7-11 carbons, acryloyloxy, methacryloyloxy, aryloxy of6-10 carbons, aralkyl of 7-10 carbons, aryloxycarbonyl of 7-11 carbons,aryl of 6-10 carbons, amino, hydroxy, carboxy, nitrile, chloro, bromo,epoxy, vinyl, alkyl mercapto of 1-4 carbons, benzoyloxy, aryl mercaptoof 6-10 carbons, alkylamino of 1-4 carbons, dialkylamino of 2-8 carbons,arylamino of 6-10 carbons, aryl alkyl amino of 7-10 carbons ortrialkoxysilyl of 3carbons.
 8. The stabilized polymeric composition ofclaim 1 wherein for the compound, when s is at least 1, R⁸ is apolymeric or copolymeric radical containing recurring units ##STR44##wherein R²⁴ is hydrogen, alkyl of 1-4 carbons and phenyl;R²⁵ is --O--,--N(R²⁶)--, --CH₂ --O--, --C(═O)--O--13 CH₂ --CH(OH)--CH₂ --O--,--C(═O)--O--CH₂ --CH₂ --O-- or --C(═O)--O--CH₂ --CH₂ --CH₂ --O--; R²⁶ ishydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted aryl of 6-10 carbons, substituted orunsubstituted araliphatic of 7-22 carbons or substituted orunsubstituted alicyclic of 5-12 carbons; the symbol ˜ represents thepolymer or copolymer backbone in which the units recur with theunderstanding that any valence not satisfied by attachment to the acylgroup of formula I is satisfied by a group R¹⁵ ; R¹⁵ is hydrogen,substituted or unsubstituted aliphatic of 1-20 carbons, substituted orunsubstituted aryl of 6-10 carbons, substituted or unsubstitutedaraliphatic of 7-22 carbons and substituted or unsubstituted alicyclicof 5-12 carbons, substituted or unsubstituted aliphatic acyl of 1-20carbons, substituted or unsubstituted alicyclic acyl of 6-14 carbons,substituted or unsubstituted aryl acyl of 7-11 carbons or substituted orunsubstituted araliphatic acyl of 7-22 carbons; wherein the substituentsfor R¹⁵ and R²⁶ independently are one or more of aliphatic of 1-8carbons, alkoxy of 1-4 carbons, alkanoyl of 1-12 carbons, alkanoyloxy of1-12 carbons, alkoxycarbonyl of 2-5 carbons, arylcarbonyl of 7-11carbons, acryloyloxy, methacryloyloxy, aryloxy of 6-10 carbons, aralkylof 7-10 carbons, aryloxycarbonyl of 7-11 carbons, aryl of 6-10 carbons,amino, hydroxy, carboxy, nitrile, chloro, bromo, epoxy, vinyl, alkylmercapto of 1-4 carbons, benzoyloxy, aryl mercapto of 6-10 carbons,alkylamino of 1-4 carbons, dialkylamino of 2-8 carbons, arylamino of6-10 carbons, aryl alkyl amino of 7-10 carbons or trialkoxysilyl of 3-9carbons.
 9. The stabilized polymeric composition of claim 1 wherein thecompoundisN-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(aminocarbonyl)phthalimide;N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(ethoxycarbonyl)phthalimide;N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(2,2,6,6-tetramethyl-4-piperidinyloxycarbonyl)phthalimide;N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-[(2-ethylhexyloxy)carbonyl]phthalimide;N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(dodecylaminocarbonyl)phthalimide;N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(dibutylaminocarbonyl)phthalimide;N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(2,2,6,6-tetramethyl-4-piperidinylaminocarbonyl)phthalimide;styrene/allylalcohol/N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-allyloxycarbonylphthalimidecopolymer; 4,4'-[2,5-dioxa-1,6-dioxohexane-1,6-diyl]bis[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide];4,4'-[1,3-phenylenedi(oxycarbonyl)] bis[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide];N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-[octylphenoxypoly(ethoxy)carbonyl]phthalimide;N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(allyloxycarbonyl)phthalimide;N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide-4-carbonyl endcappedpoly (butadiene)diol;N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-[(4-morpholinyl)carbonyl]phthalimide;N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-([4-(2,2-di(methoxycarbonyl)ethenyl)phenoxy]carbonyl)phthalimideN-(2,2,6,6-tetramethyl-4-piperidinyl)-4-([2-hydroxy-3-(alkyl[C₁₂₋₁₄]oxy)propoxy]carbonyl)phthalimide;N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(n-butoxy-carbonyl phthalimide;N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-(n-octadecyloxycarbonyl)phthalimideN-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide-4-carboxamido endcappedpolypropylene oxide;N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide-4-carbonyl endcappedhydroxy-terminated aliphatic polycarbonate;N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide-4-carbonyl endcappedaliphatic polycaprolactone diol;N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide-4-carbonyl endcappedpoly (ethylene glycol)monomethyl ether;N-(2,2,6,6-tetramethyl-4-piperidinyl)-4-[(2-hydroxy-2-phenylethoxy)carbonyl]phthalimide;4.4'-[4,13-dihydroxy-1,16-dioxo-2,6,11,15-tetraoxahexadecane-1,16-diyl]bis[N-(2,2,6,6-tetramethyl-4-piperidinyl)phthalimide]N-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-4-(ethoxycarbonyl)phthalimide;or 4.4'-(4-acetoxy-2,6-dioxa-1,7-dioxoheptane-1,7-diyl)bis[N-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)phthalimide].